CN103357276B - 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 oil-water separation mesh film and its preparation method and application in air with super parents and 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, start the upsurge of this global problem of oily waste water treatment.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 directly contact with oils all contain oil with water.Oil has the difference of polar oil and non-polar oil, and polar oil derives from animal, 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 halomereid growth, destroy marine ecology balance.Super hydrophilic super oleophobic film has in air super hydrophilic, super hydrophilic super oleophobic properties in water, when oily waste water contact membranes surface, under the stimulation of water film surface occur re-assemble from super-hydrophobic become super hydrophilic, thus water can only down permeate endlessly under gravity and capillary force effect, and surface remains super oleophobic property, oil is stayed surface always thus is reached the effect of water-oil separating, and due to the potential oil repellency of film, oil all the time cannot polluted membrane surface, be a kind of real antipollution, Non-energy-consumption, long-life, high efficiency diffusion barrier.And when the surface of film has hydrophilic polymer molecule brush, the surface hydrophilicity of film can be better, simultaneously, because hydrophilic polymer molecule brush is in the structure of full extension in water, thus make the surface of film be provided with again nano level fluff structures on the basis with micro-nano binary coarse structure, thus there is the automatically cleaning effect of similar lotus leaf surface, to greasy dirt, there is " upspringing " effect.
Publication number is that the Chinese invention patent application of CN102029079A discloses the oil-water separating net with 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 UV curing technology, the reaction time of this patent report is 60 ~ 100min, and preparation method is simple not, and containing acrylic compounds volatile reactive diluent, irritant to skin, mucous membrane and eyes, and cause larger VOC.Publication number is that the Chinese patent application of CN102716676A discloses the method with shitosan preparation with the oil-water separating net of super oleophobic properties under water, but does not relate to organic inorganic hybridization.And this film forming matter used by two patents is all completely water-soluble polymer, causes the resistance to water of nethike embrane poor.
Summary of the invention
The object of the invention is to prepare a kind of have in atmosphere and under water super hydrophilic while super oleophobic properties under water the super hydrophilic and super oleophobic water-oil separating film and preparation method thereof under water of profit UV solidification.
Another object of the present invention is to provide the super hydrophilic and application of super oleophobic water-oil separating film in the water-oil separating of oil-water separation mixture with process oil-polluted water under water of UV solidification.
It is of the present invention that to have super oil-water separation mesh film that is hydrophilic and super oleophobic properties under water be using 100 ~ 300 object screen of fabric as base material, the method of dip-coating or spraying is adopted to adsorb the water-borne UV-curing hybridization coating of one deck above, then with ultraviolet light polymerization, it is made to be coated with the hydrophilic polymer clad doped with inorganic nano-particle of micron thickness, there is the projection of nanoscale simultaneously on clad, thus obtain a kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water.
Oil-water separation mesh film of the present invention has special nanometer and the composite construction of micron, the mesh of micro-meter scale, the You Ji of micron thickness ?the raised structures of nano-scale on inorganic doping clad and clad, oil-water separation mesh film of the present invention is 0 ° at the contact angle of air to water and oil, but has super oleophobic properties under water.
The object of the invention is achieved through the following technical solutions:
UV solidifies super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, comprises the steps:
(1) by 100 ~ 300 object screen of fabric ultrasonic cleaning, normal temperature dries;
(2) adopt Rong Jiao ?gel method, with tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide for raw material, with alcohols and water in mass ratio 1:5 ~ 5:1 be mixed with cosolvent, by raw material and cosolvent in mass ratio 1:1 ~ 1:5 be mixed in 20 ~ 80 DEG C of waters bath with thermostatic control, stirring, after 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 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 solidify oligomer; 10 ~ 20 parts of multifunctional UV solidify oligomer, the Nano sol of 200 ~ 500 parts of step (2) gained, 1 ~ 5 part of light trigger and 1 ~ 5 part of emulsifying agent and mix, and disperse 10 ~ 20min with ultrasonic disperse or disk disperser under 1000 ~ 2000r/min; Obtain 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) silk screen obtained in step (1) is immersed in the UV solidified aqueous coating in step (3), after soaking 5 ~ 20min, it is vertically lifted, or adopt high-pressure spray gun to be directly sprayed on silk screen by UV solidified aqueous coating; Silk screen after immersion or spraying is hung in constant-temperature vacuum baking oven and maintains the temperature at 80 ~ 120 DEG C of oven dry, then under uv cure machine, solidify 3 ~ 5min, obtain super oil-water separation mesh film that is hydrophilic and 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 disperse is 20 ~ 40KHz, and power bracket is 300 ~ 500W.Described ultrasonic cleaning is first clean by ultrasonic washing with clean water, then with absolute ethyl alcohol or acetone ultrasonic cleaning, then uses distilled water ultrasonic cleaning clean.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 described Nano sol controls at 10 ~ 500nm, and nano particle mass content is 20 ~ 35%.
Super oil-water separation mesh film that is hydrophilic and super oleophobic under water, it is obtained by preparation method described in above-mentioned any one.Described oil-water separation mesh film is the hydrophilic polymer clad doped with inorganic nano-particle being coated with micron thickness in 100 ~ 300 object screen of fabric, it is the spherical protuberances being uniform-distribution with micro-meter scale at many levels on clad simultaneously, on micro-meter scale projection and be uniform-distribution with the spherical protuberances of nanoscale in 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 oil-water separation mesh film in atmosphere to water and oil contact angle be 0 °, under water 150 ° are greater than to the contact angle of oil droplet.
Simple function UV of the present invention solidifies oligomer, difunctionality UV solidifies oligomer and sense UV solidification oligomer is hydrophily or water-soluble oligomer; Wherein single functionality oligomer mainly forms hydrophilic polymer molecule brush on the surface of film; Bifunctionality oligomer is main film forming substance; Polyfunctionality oligomer is crosslinking agent, is conducive to forming network structure.
The invention provides the described application of oil-water separation mesh film that is super hydrophilic and super oleophobic under water in the separation of oil water mixture and the process of 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, lubrication wet goods.
Inorganic nano-particle rich surface hydroxyl of the present invention, and not containing 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.
Relative to prior art, tool of the present invention has the following advantages:
1) the simple function oligomer in Photocurable oligomers of the present invention defines polymer molecule brush on the surface of film after film-forming, thus makes the hydrophilic effect of film better, and under water, hydrophilic polymer molecule brushing tool has fabulous oil resistant adhesiving effect simultaneously.
2) the water-oil separating film prepared by the present invention carries out water-oil separating and relies on gravity and capillary force completely, thus have with low cost, energy consumption is lower, good separating effect, speed are fast, without the need to other chemical addition agents, have no side effect and secondary pollution, automatically cleaning oil resistant drips pollution, and nethike embrane easily reclaims and repeatedly reuses, and can be used for preparing on a large scale.
3) during water-oil separating film process prepared by the present invention, water flux is large, and simple to operate, except material Transfer energy consumption, without additional energy source consumption, film surface has self-cleaning function, and be easy to cleaning and reuse, the decline of membrane flux is slow.
4) raw material that adopt of the preparation of oil-water separation mesh film of the present invention are all cheap and easy to get, and all do not have toxicity, environmental friendliness, can not cause secondary pollution, also can not produce injury to the health of operator;
5) manufacture craft of the present invention and equipment are simply, are easy to realize, are applicable to large-scale production on a large scale.
Accompanying drawing explanation
Fig. 1 is embodiment 1 rich surface hydroxyl nano silicon infrared spectrogram.
Fig. 2 is that embodiment 1 cleans 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.
Detailed description of the invention
Embodiment 1: water-borne UV-curing oligomer/Nano-meter SiO_2
2the preparation of stainless steel cloth oil-water separation mesh film
(1) by one piece of 15 × 15mm
2300 object stainless steel cloths to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 150W, 40KHz ultrasonic cleaning 8min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the ammoniacal liquor that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1ml/min instillation four-hole boiling flask, after insulation 4h, discharging prepares the Nano silica sol that particle diameter is about 10nm, and nano particle mass content is 20%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, from accompanying drawing 1 infrared spectrogram, at 3400cm
?1there is strong absworption peak at place, for Qiang Ji ?the absworption peak of OH, 930cm
?1place for silanol base Si ?the stretching vibration peak of OH, 1000 ~ 1100cm
?1locate the stretching vibration absworption peak of strong and wide absworption peak for Si ?O, this place also also exists the stretching vibration absworption peak of Si ?O ?Si (four ring bodies) simultaneously.Illustrate tetraethoxysilane all hydrolytic condensation generate the Nano-meter SiO_2 of rich surface hydroxyl
2.
(3) 10 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 60 parts of difunctionality UV solidify oligomer (Changxing, Taiwan EM226); 20 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), the Ludox of 500 parts of step (2) gained, 1 part of water-soluble photoinitiator Darocur2959 (Ciba company of Switzerland), 5 parts of emulsifying agent detergent alkylate sulphur sodium sulfonates add in 1000ml beaker and mix, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(4) 10min in mixed solution stainless steel cloth immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 3min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness at 300 order stainless steel wires on the net by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, as shown in Figure 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore, as shown in Figure 6 simultaneously; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, be dispersed with the projection of micro-nano compound structure at the surface uniform of film, wherein the particle diameter of micron ball is 1 micron, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, as shown in Figure 7.
(5) contact angle of silk screen to 3 microliters of water obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) is adopted to be respectively 91.7 ° and 0 ° in atmosphere, see accompanying drawing 2 and 3, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and No. 100 solvent naphthas are blocked on film all the time, on even most telolemma, redness does not all remain, and reaches oil-water separation.
Embodiment 2: water-borne UV-curing oligomer/Nano-meter SiO_2
2the preparation of copper mesh oil-water separation mesh film
(1) by one piece of 15 × 15mm
2100 object copper mesh immerse respectively in order in distilled water, ethanol, distilled water and respectively under 100W, 20KHz, clean 10min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 80 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the hydrochloric acid that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1ml/min instillation four-hole boiling flask, after insulation 4h, discharging prepares the Nano silica sol of particle diameter 500nm, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar.
(3) 50 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3103), 60 parts of difunctionality UV solidify oligomer (Changxing, Taiwan EM227); 10 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), the Ludox of 300 parts of step (2) gained, 5 parts of water-soluble photoinitiator Esacure KIP150 (Lamberti company), 5 parts of emulsifying agent detergent alkylate sulphur sodium sulfonates add in 500ml beaker and mix, under 300W, 20KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(4) high-pressure spray gun is adopted the mixed solution that step (3) obtains to be sprayed at the clean copper mesh surface of step (1) under the pressure of 0.6Mpa, to ensure that silk screen surface uniform distributes the coating of one deck 10 microns, hanging over temperature is toast 30min in the vacuum drying oven of 120 DEG C, then nethike embrane is put into uv cure machine solidification 5min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) to the contact angle of 3 microliters of water in atmosphere, similar with 3 to accompanying drawing 2 respectively, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and diesel oil is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 3: water-borne UV-curing oligomer/Nano-meter SiO_2
2the preparation of aluminium wire netting oil-water separation mesh film
(1) by one piece of 15 × 15mm
2200 object aluminium wire nettings to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 150W, 40KHz ultrasonic cleaning 10min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetramethoxy-silicane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the sodium acid carbonate that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1.5ml/min instillation four-hole boiling flask, after insulation 5h, discharging prepares the Nano silica sol of particle diameter 200nm, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3103), 80 parts of difunctionality UV solidify oligomer (Changxing, Taiwan EM326); 20 parts of multifunctional UV solidify oligomer (Changxing, Taiwan EM2386), the Ludox of 300 parts of step (2) gained, 5 parts of water-soluble photoinitiator Irgacure891DW (Ciba Specialty Chemicals), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in 500ml beaker and mix, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(4) 10min in mixed solution aluminium wire netting immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 3min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water in atmosphere, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and dodecane is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 4: water-borne UV-curing oligomer/Nano-meter SiO_2
2the preparation of nylon mesh oil-water separation mesh film
(1) by one piece of 15 × 15mm
2300 object nylon mesh to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 100W, 20KHz ultrasonic cleaning 10min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the sulfuric acid that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1.5ml/min instillation four-hole boiling flask, after insulation 4h, the Nano silica sol that particle diameter is about about 20nm is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV solidify oligomer (Changxing, Taiwan EM327); 20 parts of multifunctional UV solidify oligomer (Qing Te company IRR210), the Ludox of 200 parts of step (2) gained, 5 parts of water-soluble photoinitiator WB ?4784 (Ward ?Blenkinsop company of Britain), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in 500ml beaker and mix, under 300W, 20KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(4) 10min in mixed solution nylon mesh immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 5min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water in atmosphere, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and rapeseed oil is blocked on film all the time, on most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 5: water-borne UV-curing oligomer/Nano-meter SiO_2
2the preparation of polyvinyl silk screen oil-water separation mesh film
(1) by one piece of 15 × 15mm
2300 object polyvinyl silk screens to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 100W, 20KHz ultrasonic cleaning 5min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the nitric acid that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1.5ml/min instillation four-hole boiling flask, after insulation 4h, the Nano silica sol that particle diameter is about about 50nm is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar;
(3) 10 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3101), 80 parts of difunctionality UV solidify oligomer (Qing Te company EB2002); 20 parts of multifunctional UV solidify oligomer (BASF AG PE55WN), the Ludox of 400 parts of step (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 500ml beaker and mix, under disk disperser, disperse 15min to ensure to be uniformly dispersed with rotating speed 1000r/min;
(4) 10min in mixed solution polyvinyl silk screen immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 5min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water in atmosphere, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and trimethylbenzene is blocked on film all the time, on most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 6: water-borne UV-curing oligomer/nano-TiO
2the preparation of aramid fiber silk screen oil-water separation mesh film
(1) by one piece of 15 × 15mm
2300 object aramid fiber silk screens to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 100W, 20KHz ultrasonic cleaning 10min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g purity titanium tetraethoxide, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take 0.5g mass concentration be 25% NaOH add in 30g deionized water, with constant flow pump with in the speed of 1.5ml/min instillation four-hole boiling flask, after insulation 4h, the nano-titanium colloidal sol that particle diameter is about about 50nm is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV solidify oligomer (Qing Te company EB11); 20 parts of multifunctional UV solidify oligomer (lid Si Tafu company 2000), the Ludox of 400 parts of step (2) gained, 5 parts of water-soluble photoinitiator WB ?4789 (Ward ?Blenkinsop company of Britain), 1 part of emulsifying agent detergent alkylate sulphur sodium sulfonate add in 500ml beaker and mix, under disk disperser, disperse 10min to ensure to be uniformly dispersed with rotating speed 1500r/min;
(4) 10min in mixed solution aramid fiber silk screen immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 5min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water in atmosphere, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, 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 water permeates downwards continually, and methyl methacrylate is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 7: water-borne UV-curing oligomer/nano-TiO
2the preparation of terylene silk net oil-water separation mesh film
(1) by one piece of 15 × 15mm
2300 object terylene silk nets to immerse respectively in order in distilled water, ethanol or acetone, distilled water each under 150W, 40KHz ultrasonic cleaning 10min, hang up and dry at normal temperatures;
(2) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, to be mixed evenly after, take the boric acid that 0.5g mass concentration is 25%, add in 30g deionized water, with constant flow pump with in the speed of 1.5ml/min instillation four-hole boiling flask, after insulation 4h, the nano-titanium colloidal sol that particle diameter is about about 50nm is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle synthesized by the test of Fourier's infrared tester, resulting structures figure and Fig. 1 is similar;
(3) 20 parts of simple function UV are solidified oligomer (Changxing, Taiwan EM3102), 80 parts of difunctionality UV solidify oligomer (Changxing EM327); 20 parts of multifunctional UV solidify oligomer (the modest UV of moral ?14), the Ludox of 400 parts of step (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 500ml beaker and mix, under 300W, 20KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(4) 10min in mixed solution terylene silk net immersion step (3) that step (1) is cleaned obtained, to ensure that silk screen is fully soaked into, then vertical lift gets up to hang over temperature is toast 30min in the vacuum drying oven of 80 DEG C, then nethike embrane is put into uv cure machine solidification 5min.
Adopt the contact angle of Dataphysics OCA40Micro type surface contact angle tester test water on nethike embrane, with the surface topography of HIT S ?3700N type sem observation nethike embrane and relative dimensions.The hydrophilic polymer clad doped with inorganic nano-particle being coated with 50 micron thickness on 300 order copper mesh by the surface of film in the visible oil-water separation mesh film of scanning electron microscope (SEM) photograph that multiplication factor is 200 times, similar to shown in Fig. 5; In silk screen interval, there is the micropore of 40 micron pore size as seen in the multiplication factor scanning electron microscopic picture that is 1000 times, be all the projection of the thick just structure of micro-nano around micropore simultaneously, similar to shown in Fig. 6; Further amplification, be that the scanning electron microscopic picture of 10000 times is visible in multiplication factor, the projection of micro-nano compound structure is dispersed with at the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 7.
(5) adopt the silk screen obtained in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water in atmosphere, prove that this nethike embrane has super hydrophilicity.
(6) silk screen obtained in step (4) is fixed in general water-oil separating membrane module, water red ink is dyed redness, with hexadecane 4:1 mixing and stirring by volume, add 0.2g neopelex, magnetic agitation 15min makes O/W emulsion, emulsion is poured in this water-oil separating membrane module, hydrophilic polymer water absorption and swelling, red water permeates downwards continually, and hexadecane is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Claims (10)
1.UV solidifies super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, it is characterized in that comprising the steps:
(1) by 100 ~ 300 object screen of fabric ultrasonic cleaning, normal temperature dries;
(2) adopt Rong Jiao ?gel method, with tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide for raw material, with alcohols and water in mass ratio 1:5 ~ 5:1 be mixed with cosolvent, by raw material and cosolvent in mass ratio 1:1 ~ 1:5 be mixed in 20 ~ 80 DEG C of waters bath with thermostatic control, stirring, after 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 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 solidify oligomer; 10 ~ 20 parts of multifunctional UV solidify oligomer, the Nano sol of 200 ~ 500 parts of step (2) gained, 1 ~ 5 part of light trigger and 1 ~ 5 part of emulsifying agent and mix, and disperse 10 ~ 20min with ultrasonic disperse or disk disperser under 1000 ~ 2000r/min; Obtain 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 Darocur 2959, Esacure KIP 150, QTX, BTC, BPQ, WB ?4784, WB ?4785, WB ?4789 or WB ?4792; Described emulsifying agent is neopelex;
(4) silk screen obtained in step (1) is immersed in the UV solidified aqueous coating in step (3), after soaking 5 ~ 20min, it is vertically lifted, or adopt high-pressure spray gun to be directly sprayed on silk screen by UV solidified aqueous coating; Silk screen after immersion or spraying is hung in constant-temperature vacuum baking oven and maintains the temperature at 80 ~ 120 DEG C of oven dry, then under uv cure machine, solidify 3 ~ 5min, obtain super oil-water separation mesh film that is hydrophilic and super oleophobic under water.
2. UV according to claim 1 solidifies super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, 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 super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, 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 super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, it is characterized in that: the supersonic frequency of described ultrasonic disperse is 20 ~ 40KHz, and power bracket is 300 ~ 500W.
5. UV according to claim 1 solidifies super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, it is characterized in that: described ultrasonic cleaning is for first clean by ultrasonic washing with clean water, then with absolute ethyl alcohol or acetone ultrasonic cleaning, then use distilled water ultrasonic cleaning clean.
6. UV according to claim 1 solidifies super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, 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 super preparation method that is hydrophilic and super oleophobic water-oil separating film under water, and it is characterized in that: the nano particle diameter in described Nano sol controls at 10 ~ 500nm, nano particle mass content is 20 ~ 35%.
8. the super hydrophilic and super oleophobic water-oil separating film under water of UV according to claim 1 solidification, is characterized in that, its by claim 1 ?preparation method described in 7 any one obtain.
9. the super hydrophilic and super oleophobic water-oil separating film under water of UV according to claim 8 solidification, it is characterized in that, described oil-water separation mesh film is the hydrophilic polymer clad doped with inorganic nano-particle being coated with micron thickness in 100 ~ 300 object screen of fabric, it is the spherical protuberances being uniform-distribution with micro-meter scale at many levels on clad simultaneously, on micro-meter scale projection and be uniform-distribution with the spherical protuberances of nanoscale in 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 oil-water separation mesh film in atmosphere to water and oil contact angle be 0 °, under water 150 ° are greater than to the contact angle of oil droplet.
10. the UV described in claim 8 or 9 solidifies the super hydrophilic and application of super oleophobic water-oil separating film in the separation of oil water mixture and the process of oil-polluted water under water.
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| CN105148563B (en) * | 2015-08-12 | 2017-03-22 | 华南农业大学 | Superhydrophilic and superoleophobic oil-water separation membrane with humidity responsiveness as well as preparation method and application of oil-water separation membrane |
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| CN107115794B (en) * | 2017-05-17 | 2019-12-03 | 江苏大学 | One step constructs the method and its application of super-hydrophobic water-oil separationg film |
| CN107080976A (en) * | 2017-06-15 | 2017-08-22 | 河北工业大学 | A kind of preparation method with the oil-water separation mesh film of superoleophobic property under water |
| CN110917896A (en) * | 2019-12-04 | 2020-03-27 | 中国矿业大学 | Preparation method of composite filter membrane capable of selectively filtering low-density lipoprotein in hyperlipemia blood |
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