CN103893999A - Super-hydrophilic and underwater super-oleophobic oil-water separation mesh film and preparation method thereof - Google Patents
Super-hydrophilic and underwater super-oleophobic oil-water separation mesh film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophilic and underwater super-oleophobic oil-water separation mesh film and a preparation method thereof. The method comprises the following steps: ultrasonically cleaning a fabric silk screen and airing at normal temperature; preparing polymer emulsion particle microspheres of which the particle size distribution is 100-500nm and the surface is rich in carboxyl salt by adopting an emulsion polymerization, and preparing nano-silica sol by adopting a sol-gel method; preparing hydrophilic emulsion particles and the nano sol into a mixed solution and performing uniformly ultrasonic dispersion; immersing the silk screen into the mixed solution, vertically lifting up, or directly spraying by adopting a high-pressure spray gun, and drying to obtain the super-hydrophilic and underwater super-oleophobic oil-water separation mesh film. The surface of the oil-water separation mesh film has a spherical rough micro-nano binary structure, contact angles with water and oil in air are 0 degree, and the oil-water separation mesh film has the super hydrophilicity. A contact angle with oil drops under water is larger than 150 degrees, and the oil-water separation mesh film has low adhesion properties on the oil drops. The mesh film can be applied to separating oil water mixtures and treating oily sewage.
Description
Technical field
The present invention relates to new type functional environmental protection coating material, particularly relate to a kind of rich surface containing the polyalcohol emulsion particle microballoon of carboxylic salts and a kind ofly there is super parents in air and the water-oil separating nethike embrane and its preparation method and application of super oleophobic properties under water, belonging to organic-inorganic hybrid nanometer technical field of function materials.
Background technology
Super hydrophilic super oleophobic film has in air super hydrophilic, super hydrophilic super oleophobic properties in water, in the time of oily waste water contact membranes surface, under the stimulation of water film surface occur re-assemble from super-hydrophobic become super hydrophilic, thereby water can only down permeate endlessly under gravity and capillary force effect, and surface remains super oleophobic property, thereby the effect of water-oil separating stayed surface always and reaches by oil, and due to the potential oil repellency of film, oil all the time cannot polluted membrane surface, is a kind of real antipollution, Non-energy-consumption, long-life, high efficiency diffusion barrier.Aspect raw material, the super hydrophilic membrane of preparation is mainly used three kinds of thinkings, i.e. single hydrophilic polymer, hydrophilic polymer grafting low energy segment or fluoropolymer grafting hydrophilic segment at present.Single hydrophilic polymer exists because of the very good poor water resistance that makes film of polymer water dissolubility, and polymer is dissolved away or makes the phenomenon of Pore Blocking because of water absorption and swelling; A large amount of uses are fluoridized POSS, are fluoridized the fluorine materials such as amphipathic polymer, and preparation difficulty is expensive, cannot assess at present the impact of environment, is difficult to widely apply in practice.
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, the reaction time be 60 ?100min, preparation method is simple not.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 patent film forming matters used are all complete water-soluble polymer, cause the resistance to water of nethike embrane poor.
Summary of the invention
The object of the invention is to prepare and a kind ofly have in air and the water-oil separating nethike embrane and preparation method thereof of super oleophobic properties under water of super hydrophilic while under water.
Another object of the present invention is to provide the application of super water-oil separating nethike embrane hydrophilic and super oleophobic under water in the water-oil separating of oil-polluted water.
It is of the present invention that to have super water-oil separating nethike embrane hydrophilic and super oleophobic properties under water be using 100 ?300 object screen of fabric as base material, adopt the method for dip-coating or spraying to be coated with the rich surface doped with inorganic nano-particle of micron thickness in the above containing the polyalcohol emulsion particle microballoon clad of carboxylic salts, on clad, there is the projection of nanoscale, thereby obtain a kind of super water-oil separating nethike embrane hydrophilic and super oleophobic under water simultaneously.
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 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:
A preparation method for super water-oil separating nethike embrane hydrophilic and super oleophobic under water, comprises the steps:
1) by 100 ?300 object screen of fabric ultrasonic cleaning, normal temperature dries;
2) preparation of seed emulsion: in mass fraction, by 50 ?100 parts of deionized waters and 0.0126 ?0.0252 part of emulsifier for mixing mix, be warming up to 85 ?90 ℃, then add 0.2 ?0.4 part of initator, 0.225 ?0.45 part of carboxylic monomer and 2.2 ?4.4 parts of styrene mixture, stir, react 1 ?be incubated after 1.5h, obtain seed emulsion;
3) preparation of nuclear emulsion grain: in mass fraction, by 100 ?120 parts of deionized waters, 100 ?122 parts of styrene and 3 ?6 parts of chain-transferring agent agitating heating be warming up to 85 ?90 ℃, in 1h, slowly add in described seed emulsion;
4) He ?the preparation of shell polymeric emulsion particle microballoon: in mass fraction, containing in described nuclear emulsion grain solution, add 100 ?120 parts of deionized waters and 0.8 ?the mixed liquors of 1.056 parts of initator compositions, 1 ?add in 1.5h 50 ?60 parts of deionized waters, 3 ?5 parts of emulsifying agents, 80 ?100 parts of styrene and 19 ?22 parts of crosslinking agents, react 2 ?drip after 2.5h 2 ?5 parts of carboxylic monomers, continue stir and be incubated 1 ?1.5h, rear dropping nertralizer 100% neutralizes, get He ?shell polymeric emulsion particle microballoon;
5) Cai with Rong Jiao ?gel method, take tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols material 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 80 ℃ of waters bath with thermostatic control of 20 ?, stirring, 5 ?after 10min, drip catalyst, insulation 4 ?5h, obtain Nano sol; Described alcohols material 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;
6) by step 4) in He ?shell emulsion particle and step 5) in Nano sol in mass ratio 1:9 ?the ratio of 9:1 be mixed with concentration be 1 ?99% mixed solution, ultrasonic being uniformly dispersed;
7) silk screen that obtains in step (1) is immersed to step 6) in mixed solution in, soak 5 ?it has vertically been lifted after 20min, or adopt high-pressure spray gun direct spraying, by soak or spraying after silk screen hang in constant-temperature vacuum baking oven, maintain the temperature at 100 ?200 ℃ of oven dry; Must super water-oil separating nethike embrane hydrophilic and super oleophobic under water;
For further realizing the object of the invention, described screen of fabric is preferably 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 be 20 ?40KHz, power bracket be 100 ?150W.The supersonic frequency of described ultrasonic dispersion be 20 ?40KHz, power bracket be 300 ?500W.Described ultrasonic cleaning, for 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 be preferably 1 ?10ml/min.Described He ?shell polymeric emulsion particle microballoon take styrene as main body, particle diameter be distributed in 100 ?between 500nm, microsphere surface is rich in carboxylic salts; Inorganic nano-particle rich surface hydroxyl in described Nano sol, and containing other organic groups, particle diameter be 10 ?500nm, nano particle mass content be 20 ?35%.
Super water-oil separating nethike embrane hydrophilic and super oleophobic under water, is made by above-mentioned preparation method; Described water-oil separating nethike embrane is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with micron thickness in 100 ?300 object screen of fabric, on clad, be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale simultaneously, on micro-meter scale projection and micron be uniform-distribution with the spherical protuberances of nanoscale in projection interval, the thickness of the clad of described micron thickness be 11 ?50 μ m; The spherical protuberances particle diameter of described micro-meter scale be 1 ?50 μ m; The particle diameter of the spherical protuberances of described nano-scale width be 10 ?900nm; The aperture of the mesh of described micro-meter scale be 30 ?170 μ m; The aperture of the mesh of described micro-meter scale be 10 ?100 μ m; The thickness of the clad of described micron thickness be 11 ?50 μ m; The height of the projection of described nano-scale width be 10 ?900nm; Described water-oil separating nethike embrane is 0 ° to water and oily contact angle in air, under water the contact angle of oil droplet is greater than to 150 °.
The application of water-oil separating nethike embrane super hydrophilic and super oleophobic under water described in the present invention also provides in the water-oil separating of oil-polluted water; Contain 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 as can be used for; 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.
With respect to prior art, tool of the present invention has the following advantages:
1) the prepared water-oil separating film of the present invention carries out water-oil separating and relies on gravity and capillary force completely, thereby have with low cost, energy consumption is lower, good separating effect, speed are fast, without 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.
2) the present invention does not use hydrophilic polymer, and polymer microballoon used is take styrene as main body, and just rich surface is containing carboxylic salts, and therefore, it is hydrophobic in essence, and surface hydrophilic, thus after film forming hydrophily and resistance to water fabulous.
3) when the prepared water-oil separating film of the present invention is processed, water flux is large, simple to operate, and except material Transfer energy consumption, without additional energy source consumption, film surface has self-cleaning function, is easy to clean and recycling, and the decline of membrane flux is slow.
4) raw material that the preparation of water-oil separating nethike embrane of the present invention adopts are all cheap and easy to get, and all there is no toxicity, and environmental friendliness can not cause secondary pollution, also can not produce injury to operator's health; Manufacture craft of the present invention and equipment are simple, are easy to realize, and are applicable to large-scale production on a large scale.
Accompanying drawing explanation
Fig. 1 is 150000 times of SEM figure of the prepared emulsion particle of embodiment 1.
Fig. 2 is 100000 times of TEM figure of the prepared emulsion particle of embodiment 1.
Fig. 3 is embodiment 1 rich surface hydroxyl nanometer SiO
2infrared spectrogram.
Fig. 4 is that 10000 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 5 is the clean blank stainless steel cloth surface water contact angle (91.3 °) of embodiment 1.
Fig. 6 is embodiment 1 micro-nano structure stainless steel cloth film coated surface water contact angle (0 °).
The specific embodiment
For understanding better the present invention, below in conjunction with embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) by a 15 × 15mm
2300 object stainless steel cloths immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 8min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 100g deionized water and 0.0252gSDBS, stir and be warming up to gradually 90 ℃, then by 0.4g sodium peroxydisulfate, disposable the adding of mixture of 0.45g acrylic acid and 4.4g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 120g deionized water in 1000ml four-hole boiling flask, 122g styrene, and 6g lauryl mercaptan, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 120g deionized water, 1.056g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 60g deionized water, 5g DNS ?458,100g styrene, 22gDVB, after reaction 2h, drip 5g acrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, respectively as depicted in figs. 1 and 2.As seen from the figure gained He ?shell polymeric emulsion particle micro-sphere structure be regular spherical of form, particle diameter is evenly distributed, and is approximately distributed in 200nm left and right, and is uniformly dispersed, without bonding.
(5) 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 0.5g mass concentration and be 25% ammoniacal liquor, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1ml/min with constant flow pump, after insulation 4h, discharging prepares the Nano silica sol of the about 10nm of particle diameter, and nano particle mass content is 20%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, the sample of twice different experiments is tested respectively, and gained infrared spectrum curve is shown in respectively in accompanying drawing 3 shown in curve 1 and 2, from accompanying drawing 3 infrared spectrograms, curve obtained absworption peak overlaps completely, at 3400cm
?1there is a 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 strong and wide absworption peak 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.
(6) be that 1:1 mixes by the emulsion particle solution in step (4) and step (5) gained Ludox by solute mass ratio, being diluted with water and being mixed with concentration is 1% solution, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed with assurance;
(7) 10min in mixed solution stainless steel cloth immersion step (6) clean step (1) being obtained, to guarantee that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.Be coated with at 300 order stainless steel wires the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick on the net; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 1 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, as shown in Figure 4.In air, with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester testing procedure (1) empty silk screen and step (7), the contact angle of 3 microliters of water is respectively to 91.7 ° and 0 °, see accompanying drawing 5 and 6, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, with No. 100 solvent naphthas 1:1 mixing and stirring by volume, oil-water mixture is poured in film, red water is infiltration downwards continually, and No. 100 solvent naphthas are blocked on film all the time, on even telolemma, redness does not all have residually, has reached oil-water separation.
Embodiment 2
(1) by a 15 × 15mm
2100 object copper mesh immerse respectively in order in distilled water, ethanol, distilled water respectively at 100W, under 20KHz, clean 10min, hang up at normal temperatures and dry;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 50g deionized water and 0.0126gSDBS, mix and blend is also warming up to 85 ℃ gradually, then by 0.2g sodium peroxydisulfate, disposable the adding of mixture of 0.225g methacrylic acid and 2.2g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 100g deionized water in 1000ml four-hole boiling flask, 100g styrene, and 3g mercaptoethanol, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 100g deionized water, 0.8g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 50g deionized water, 3g DNS ?458,80g styrene, 19g crosslinking agent DVB, after reaction 2h, drip 2g methacrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer N, N dimethylethanolamine 100% neutralize;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, respectively with similar shown in Fig. 1 and Fig. 2.
(5) 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 0.5g mass concentration and be 25% hydrochloric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1ml/min with constant flow pump, 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 of Fourier's infrared tester test synthesized, similar to Fig. 3.
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed by solute mass ratio 1:9, adding water and being mixed with concentration is 5% solution, and at 300W, under 20KHz, ultrasonic dispersion 10min is uniformly dispersed guaranteeing;
(7) mixed solution that adopts high-pressure spray gun under the pressure of 0.6Mpa, step (6) to be obtained is sprayed at the clean copper mesh surface of step (1), be to toast 30min in the constant-temperature vacuum drying box of 120 ℃ to guarantee the coating of silk screen surface uniform distribution one deck 10 μ m, to hang over temperature.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle of 50 μ m degree; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 4.In air with the silk screen that obtains in Dataphysics OCA40Micro type Surface Contact angle tester testing procedure (1) empty silk screen and step (7) contact angle to 3 microliters of water, similar with 6 to accompanying drawing 5 respectively, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, with diesel oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and diesel oil is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 3
(1) by a 15 × 15mm
2200 object aluminium wire nettings immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 100g deionized water and 0.0252gSDBS, mix and blend is also warming up to 90 ℃ gradually, then by 0.4 sodium peroxydisulfate, disposable the adding of mixture of 0.45g acrylic acid and 4.4g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 120g deionized water in 1000ml four-hole boiling flask, 122g styrene, and 6g lauryl mercaptan, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 120g deionized water, 1.056g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 60g deionized water, 5g DNS ?458,100g styrene, 22gDVB, after reaction 2h, drip 5g acrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, similar with Fig. 2 to Fig. 1 respectively.
(5) 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 0.5g mass concentration and be 25% sodium acid carbonate, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, 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 of Fourier's infrared tester test synthesized, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (3) gained Ludox are mixed by solute mass ratio 9:1, adding water and being mixed with concentration is 99% solution, and at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed guaranteeing;
(7) 8min in mixed solution aluminium wire netting immersion step (6) clean step (1) being obtained, to guarantee that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 100 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 4.Similar with 6 to accompanying drawing 5 respectively to the contact angle of 3 microliters of water with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester step (1) empty silk screen and step (7) in air, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, with dodecane 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, red water is infiltration downwards continually, and dodecane is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 4
(1) by a 15 × 15mm
2300 object nylon mesh immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 100g deionized water and 0.0252gSDBS, mix and blend is also warming up to 90 ℃ gradually, then by 0.4 sodium peroxydisulfate, disposable the adding of mixture of 0.45g acrylic acid and 4.4g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 120g deionized water in 1000ml four-hole boiling flask, 122g styrene, and 6g lauryl mercaptan, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 120g deionized water, 1.056g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 60g deionized water, 5g DNS ?458,100g styrene, 22gDVB, after reaction 2h, drip acrylic acid 5g, continue to stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, similar with Fig. 1 and Fig. 2 respectively.
(5) 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 0.5g mass concentration and be 25% sulfuric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the Nano silica sol of the about 20nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed by solute mass ratio 1:9, add water and be mixed with the solution of mass concentration 10%, at 300W, under 20KHz, ultrasonic dispersion 10min is uniformly dispersed with assurance;
(7) 10min in mixed solution nylon mesh immersion step (6) clean step (1) being obtained, to guarantee that gauze is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 100 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 4.Similar with 6 to accompanying drawing 5 respectively to the contact angle of 3 microliters of water with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester step (1) empty silk screen and step (7) in air, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, with rapeseed oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, red water is infiltration downwards continually, and rapeseed oil is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 5
(1) by a 15 × 15mm
2300 object polyvinyl silk screens immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 5min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 100g deionized water and 0.0252gSDBS, mix and blend is also warming up to 90 ℃ gradually, then by 0.4 sodium peroxydisulfate, disposable the adding of mixture of 0.45g acrylic acid and 4.4g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 120g deionized water in 1000ml four-hole boiling flask, 122g styrene, and 6g lauryl mercaptan, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 120g deionized water, 1.056g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 60g deionized water, 5g DNS ?458,100g styrene, 22gDVB, after reaction 2h, drip 5g acrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, similar with Fig. 1 and Fig. 2 respectively.
(5) 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 0.5g mass concentration and be 25% nitric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the Nano silica sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed by solute mass ratio 9:1, be mixed with concentration and be 1% solution, at 40W, under 30KHz, ultrasonic dispersion 10min is uniformly dispersed guaranteeing;
(7) 10min in mixed solution stainless steel cloth immersion step (6) clean step (1) being obtained, to guarantee that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, similar with Fig. 4.Similar with 6 to accompanying drawing 5 respectively to the contact angle of 3 microliters of water with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester step (1) empty silk screen and step (7) in air, prove that this nethike embrane has super hydrophilicity.
(7) water is dyeed with red ink, with trimethylbenzene 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, red water is infiltration downwards continually, and trimethylbenzene is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 6
(1) by a 15 × 15mm
2300 object aramid fiber silk screens immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 50g deionized water and 0.0126gSDBS, mix and blend is also warming up to 85 ℃ gradually, then by 0.2g sodium peroxydisulfate, disposable the adding of mixture of 0.225g methacrylic acid and 2.2g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 100g deionized water in 1000ml four-hole boiling flask, 100g styrene, and 3g mercaptoethanol, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 100g deionized water, 0.8g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 50g deionized water, 3g DNS ?458,80g styrene, 19g crosslinking agent DVB, after reaction 2h, drip 2g methacrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, respectively with similar shown in Fig. 1 and Fig. 2.
(5) 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 0.5g mass concentration and be 25% NaOH adds in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the nano-titanium colloidal sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, similar to Fig. 3;
(6) by the emulsion particle solution in step (4) and step (5) gained Ludox in mass ratio 1:1 mix, add water and be mixed with the solution of concentration 1%, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed guaranteeing;
(7) 10min in mixed solution stainless steel cloth immersion step (6) clean step (1) being obtained, to guarantee that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, similar with Fig. 4.Similar with 6 to accompanying drawing 5 respectively to the contact angle of 3 microliters of water with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester step (1) empty silk screen and step (7) in air, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, with methyl methacrylate 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and methyl methacrylate is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 7
(1) by a 15 × 15mm
2300 object terylene silk nets immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) preparation of seed emulsion, in 250ml four-hole boiling flask, add 50g deionized water and 0.0126gSDBS, mix and blend is also warming up to 85 ℃ gradually, then by 0.2g sodium peroxydisulfate, disposable the adding of mixture of 0.225g methacrylic acid and 2.2g styrene composition, stirs, and is incubated for subsequent use after reaction 1h;
(3) preparation of nuclear emulsion grain adds 100g deionized water in 1000ml four-hole boiling flask, 100g styrene, and 3g mercaptoethanol, agitating heating is warming up to 85 ℃, slowly adds above-mentioned seed emulsion in 1h;
(4) He ?the preparation of shell emulsion particle, containing in above-mentioned nuclear emulsion grain solution, by 100g deionized water, 0.8g sodium peroxydisulfate mixed liquor adds 50% in 75min, after in 225min, drip remaining, 1h add 50g deionized water, 3g DNS ?458,80g styrene, 19g crosslinking agent DVB, after reaction 2h, drip 2g methacrylic acid, continue to stir and be incubated 1h, rear dropping nertralizer N, N dimethylethanolamine 100% neutralize;
With the S of Hitachi, Ltd ?the form of the emulsion particle prepared of 3700N type SEM, the Quanta200 of FEI Co. type ultrahigh resolution field emission scanning electron microscope and Nova NanoSEM430 type transmission electron microscope observation, respectively with similar shown in Fig. 1 and Fig. 2.
(5) 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 0.5g mass concentration and be 25% boric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the nano-titanium colloidal sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed by solute mass ratio 1:1, adding water and being mixed with concentration is 99% solution, and at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed guaranteeing;
(7) 5min in mixed solution terylene silk net immersion step (6) clean step (1) being obtained, to guarantee that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 150 ℃.
With the S of Hitachi, Ltd ?surface topography and the relative dimensions of 3700N type sem observation nethike embrane.On 300 order copper mesh, be coated with the hydrophilic polymer clad doped with inorganic nano-particle that 50 μ m are thick; In silk screen interval, exist the micropore in 40 μ m apertures, micropore is all around the thick just projection of structure of micro-nano simultaneously; Be that the SEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 μ m, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, similar to Fig. 4.Similar with 6 to accompanying drawing 5 respectively to the contact angle of 3 microliters of water with the silk screen obtaining in Dataphysics OCA40Micro type Surface Contact angle tester step (1) empty silk screen and step (7) in air, prove that this nethike embrane has super hydrophilicity.
(8) water is dyeed with red ink, 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 film, and red water is infiltration downwards continually, and hexadecane is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Claims (9)
1. a preparation method for super water-oil separating nethike embrane hydrophilic and super oleophobic under water, is characterized in that comprising the steps:
1) by 100 ?300 object screen of fabric ultrasonic cleaning, normal temperature dries;
2) preparation of seed emulsion: in mass fraction, by 50 ?100 parts of deionized waters and 0.0126 ?0.0252 part of emulsifier for mixing mix, be warming up to 85 ?90 ℃, then add 0.2 ?0.4 part of initator, 0.225 ?0.45 part of carboxylic monomer and 2.2 ?4.4 parts of styrene mixture, stir, react 1 ?be incubated after 1.5h, obtain seed emulsion;
3) preparation of nuclear emulsion grain: in mass fraction, by 100 ?120 parts of deionized waters, 100 ?122 parts of styrene and 3 ?6 parts of chain-transferring agent agitating heating be warming up to 85 ?90 ℃, in 1h, slowly add in described seed emulsion;
4) He ?the preparation of shell polymeric emulsion particle microballoon: in mass fraction, containing in described nuclear emulsion grain solution, add 100 ?120 parts of deionized waters and 0.8 ?the mixed liquors of 1.056 parts of initator compositions, 1 ?add in 1.5h 50 ?60 parts of deionized waters, 3 ?5 parts of emulsifying agents, 80 ?100 parts of styrene and 19 ?22 parts of crosslinking agents, react 2 ?drip after 2.5h 2 ?5 parts of carboxylic monomers, continue stir and be incubated 1 ?1.5h, rear dropping nertralizer 100% neutralizes, get He ?shell polymeric emulsion particle microballoon;
5) Cai with Rong Jiao ?gel method, take tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols material 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 80 ℃ of waters bath with thermostatic control of 20 ?, stirring, 5 ?after 10min, drip catalyst, insulation 4 ?5h, obtain Nano sol; Described alcohols material 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;
6) by step 4) in He ?shell emulsion particle and step 5) in Nano sol in mass ratio 1:9 ?the ratio of 9:1 be mixed with concentration be 1 ?99% mixed solution, ultrasonic being uniformly dispersed;
7) silk screen that obtains in step (1) is immersed to step 6) in mixed solution in, soak 5 ?it has vertically been lifted after 20min, or adopt high-pressure spray gun direct spraying, by soak or spraying after silk screen hang in constant-temperature vacuum baking oven, maintain the temperature at 100 ?200 ℃ of oven dry; Must super water-oil separating nethike embrane hydrophilic and super oleophobic under water;
Described carboxylic monomer is acrylic or methacrylic acid; Described nertralizer is triethylamine or N, N dimethylethanolamine; Described emulsifying agent be SDBS or DNS ?458, described chain-transferring agent is lauryl mercaptan or mercaptoethanol; Described initator is sodium peroxydisulfate; Described crosslinking agent is DVB.
2. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, it is characterized in that: described He ?shell polymeric emulsion particle microballoon take styrene as main body, particle diameter be distributed in 100 ?between 500nm, microsphere surface is rich in carboxylic salts; Nano particle diameter in described Nano sol be controlled at 10 ?500nm, nano particle mass content be 20 ?35%.
3. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, 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.
4. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the supersonic frequency of described ultrasonic cleaning is 20 ?40KHz, and power bracket is 100 ?150W; The supersonic frequency of described ultrasonic dispersion be 20 ?40KHz, power bracket be 300 ?500W.
5. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, 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. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the speed of described dropping catalysis is 1 ?10ml/min.
7. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: described mixed liquor adds 50% in 75min, remainingly in 225min, drips.
8. super water-oil separating nethike embrane hydrophilic and super oleophobic under water, is characterized in that, it is made by preparation method described in claim 1 ?7 any one; Described water-oil separating nethike embrane is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with micron thickness in 100 ?300 object screen of fabric, on clad, be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale simultaneously, on micro-meter scale projection and micron be uniform-distribution with the spherical protuberances of nanoscale in projection interval, the thickness of the clad of described micron thickness be 11 ?50 μ m; The spherical protuberances particle diameter of described micro-meter scale be 1 ?50 μ m; The particle diameter of the spherical protuberances of described nano-scale width be 10 ?900nm; Described water-oil separating nethike embrane is 0 ° to water and oily contact angle in air, under water the contact angle of oil droplet is greater than to 150 °.
9. the application of super water-oil separating nethike embrane hydrophilic and super oleophobic under water claimed in claim 8 in the separation of oil water mixture and the processing of oil-polluted water.
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