CN103893999B - A kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water and preparation method thereof - Google Patents
A kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of super oil-water separation mesh film that is hydrophilic and super oleophobic under water and preparation method thereof.The method is by screen of fabric ultrasonic cleaning, and normal temperature dries; Adopt emulsion polymerization prepare domain size distribution in 100 the rich surface of 500nm containing the polyalcohol emulsion particle microballoon of carboxylic salts, adopt Rong Jiao gel method prepare nano silicon dioxide sol; Hydrophilic emulsion particle emulsion and Nano sol are mixed with mixed solution, and ultrasonic disperse is even; Silk screen is immersed in mixed solution, vertically lift, or adopt high-pressure spray gun direct spraying, dry, obtain super oil-water separation mesh film that is hydrophilic and super oleophobic under water.Oil-water separation mesh film surface of the present invention has spherical micro-nano binary coarse structure, is 0 ° in atmosphere, has Superhydrophilic to the contact angle of water and oil; Under water 150 ° are greater than to the contact angle of oil droplet, there is the characteristic to the low adhesion of oil droplet.Nethike embrane of the present invention can be applicable to the separation of oil water mixture and the process of oil-polluted water.
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 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 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, 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.In raw material, the super hydrophilic film of preparation mainly uses 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 also exists the poor water resistance making film because polymeric water-soluble is very good, and polymer is dissolved away or makes the phenomenon of Pore Blocking because of water absorption and swelling; A large amount of use is fluoridized POSS, is fluoridized the fluorine materials such as amphipathic polymer, preparation difficulty, expensive, cannot assess at present, be difficult to widely apply in practice on the impact of environment.
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, the reaction time be 60 ?100min, preparation method is simple not.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 oil-water separation mesh film and preparation method thereof.
Another object of the present invention is to provide the application of super oil-water separation mesh film that is hydrophilic and super oleophobic under water in the water-oil separating of oil-polluted water.
Of the present invention 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 be coated with the polyalcohol emulsion particle micro-spheres layer of the rich surface doped with inorganic nano-particle containing carboxylic salts of micron thickness above, 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:
A super preparation method that the is hydrophilic and oil-water separation mesh film of 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 ?the mixing of 0.0252 part of emulsifier for mixing, be warming up to 85 ?90 DEG C, 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 DEG C, slowly add in 1h 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 liquor of 1.056 parts of initators composition, 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) adopt Rong Jiao ?gel method, with tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide for 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 20 ?, 80 DEG C of waters bath with thermostatic control, stirring, 5 ?after 10min, drip catalyst, be incubated 4 ?5h, namely 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 proportions of 9:1 become concentration be 1 ?99% mixed solution, ultrasonic disperse is even;
7) will the silk screen that obtain in step (1) immerse step 6) in mixed solution in, soak 5 ?it is vertically lifted after 20min, or adopt high-pressure spray gun direct spraying, by soak or silk screen after spraying hang in constant-temperature vacuum baking oven maintain the temperature at 100 ?200 DEG C of oven dry; Must super oil-water separation mesh film that is hydrophilic and super oleophobic under water;
For realizing the object of the invention further, 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 disperse be 20 ?40KHz, power bracket be 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 catalyst be preferably 1 ?10ml/min.Described He ?shell polymeric emulsion particle microballoon based on styrene, domain size distribution 100 ?between 500nm, microsphere surface is rich in carboxylic salts; Inorganic nano-particle rich surface hydroxyl in described Nano sol, and not containing other organic groups, particle diameter be 10 ?500nm, nano particle mass content be 20 ?35%.
Super oil-water separation mesh film that is hydrophilic and super oleophobic under water, is obtained by above-mentioned preparation method; Described oil-water separation mesh film be 100 ?300 object screen of fabric are coated with the hydrophilic polymer clad doped with inorganic nano-particle of micron thickness, 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 be 11 ?50 μm; The spherical protuberances particle diameter of described micro-meter scale be 1 ?50 μm; 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 μm; The aperture of the mesh of described micro-meter scale be 10 ?100 μm; The thickness of the clad of described micron thickness be 11 ?50 μm; The height of the projection of described nano-scale width be 10 ?900nm; 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.
The present invention also provides the described application of oil-water separation mesh film that is super hydrophilic and super oleophobic under water in the water-oil separating 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.
Relative to prior art, tool of the present invention has the following advantages:
1) 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.
2) the present invention does not use hydrophilic polymer, and polymer microballoon used is based on styrene, and just rich surface is containing carboxylic salts, therefore, its hydrophobic in nature, and surface hydrophilic, thus after film forming hydrophily and resistance to water fabulous.
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; Manufacture craft of the present invention and equipment simply, are easy to realize, are applicable to large-scale production on a large scale.
Accompanying drawing explanation
150000 times of SEM figure of the emulsion particle of Fig. 1 prepared by embodiment 1.
100000 times of TEM figure of the emulsion particle of Fig. 2 prepared by embodiment 1.
Fig. 3 is embodiment 1 rich surface hydroxyl Nano-meter SiO_2
2infrared spectrogram.
Fig. 4 is that 10000 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 5 is that embodiment 1 cleans blank stainless steel cloth surface water contact angle (91.3 °).
Fig. 6 is embodiment 1 micro-nano structure stainless steel cloth film coated surface water contact angle (0 °).
Detailed description of the invention
For understanding the present invention better, below in conjunction with embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited thereto.
Embodiment 1
(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) preparation of seed emulsion, in 250ml four-hole boiling flask, add 100g deionized water and 0.0252gSDBS, stir and be warming up to 90 DEG C gradually, then by 0.4g sodium peroxydisulfate, the mixture of 0.45g acrylic acid and 4.4g styrene composition is disposable to add, and 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, 6g lauryl mercaptan, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 60g deionized water, 5gDNS ?458,100g styrene, 22gDVB, reaction 2h after drip 5g acrylic acid, continue stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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, even particle size distribution, is approximately distributed in about 200nm, and is uniformly dispersed, without bonding.
(5) 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, tested respectively by the sample of twice different experiments, gained infrared spectrum curve is shown in accompanying drawing 3 shown in curve 1 and 2 respectively, from accompanying drawing 3 infrared spectrogram, curve obtained absworption peak overlaps completely, 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.
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed than for 1:1 by Solute mass, be diluted with water and be mixed with the solution that concentration is 1%, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 10min in mixed solution stainless steel cloth immersion step (6) 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 150 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle are coated with on the net at 300 order stainless steel wires; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 1 μm, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, as shown in Figure 4.91.7 ° and 0 ° is respectively in atmosphere with the contact angle of silk screen to 3 microliters of water obtained in DataphysicsOCA40Micro type surface contact angle tester testing procedure (1) empty silk screen and step (7), see accompanying drawing 5 and 6, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, with No. 100 solvent naphthas 1:1 mixing and stirring by volume, oil-water mixture is poured in film, 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
(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) 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 DEG C gradually, then by 0.2g sodium peroxydisulfate, the mixture of 0.225g methacrylic acid and 2.2g styrene composition is disposable to add, and 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, 3g mercaptoethanol, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 50g deionized water, 3gDNS ?458,80g styrene, 19g crosslinking agent DVB, reaction 2h after drip 2g methacrylic acid, continue stir and be incubated 1h, rear dropping nertralizer N, N dimethylethanolamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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 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, similar to Fig. 3.
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed than 1:9 by Solute mass, add water and be mixed with the solution that concentration is 5%, under 300W, 20KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) high-pressure spray gun is adopted the mixed solution that step (6) 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 μm, hanging over temperature is toast 30min in the vacuum drying oven of 120 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with the hydrophilic polymer clad doped with inorganic nano-particle of 50 μm of degree; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to shown in Fig. 4.In atmosphere with the silk screen obtained in DataphysicsOCA40Micro type surface contact angle tester testing procedure (1) empty silk screen and step (7) to the contact angle of 3 microliters of water, similar with 6 to accompanying drawing 5 respectively, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, 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 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
(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) 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 DEG C gradually, then by 0.4 sodium peroxydisulfate, the mixture of 0.45g acrylic acid and 4.4g styrene composition is disposable to add, and 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, 6g lauryl mercaptan, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 60g deionized water, 5gDNS ?458,100g styrene, 22gDVB, reaction 2h after drip 5g acrylic acid, continue stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 type transmission electron microscope observation, similar to Fig. 1 with Fig. 2 respectively.
(5) 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, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (3) gained Ludox are mixed than 9:1 by Solute mass, add water and be mixed with the solution that concentration is 99%, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 8min in mixed solution aluminium wire netting immersion step (6) 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 60min in the vacuum drying oven of 100 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with 50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to 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 obtained in DataphysicsOCA40Micro type surface contact angle tester step (1) empty silk screen and step (7) in atmosphere, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, with dodecane 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, 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
(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) 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 DEG C gradually, then by 0.4 sodium peroxydisulfate, the mixture of 0.45g acrylic acid and 4.4g styrene composition is disposable to add, and 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, 6g lauryl mercaptan, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 60g deionized water, 5gDNS ?458,100g styrene, 22gDVB, reaction 2h after drip acrylic acid 5g, continue stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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 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, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed than 1:9 by Solute mass, add water and be mixed with the solution of mass concentration 10%, under 300W, 20KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 10min in mixed solution nylon mesh immersion step (6) that step (1) is cleaned obtained, to ensure that gauze is fully soaked into, then vertical lift gets up to hang over temperature is toast 60min in the vacuum drying oven of 100 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with 50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is the nanosphere that particle diameter is 100nm between micron ball interval, similar to 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 obtained in DataphysicsOCA40Micro type surface contact angle tester step (1) empty silk screen and step (7) in atmosphere, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, with rapeseed oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, red water permeates downwards continually, and rapeseed oil is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 5
(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) 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 DEG C gradually, then by 0.4 sodium peroxydisulfate, the mixture of 0.45g acrylic acid and 4.4g styrene composition is disposable to add, and 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, 6g lauryl mercaptan, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 60g deionized water, 5gDNS ?458,100g styrene, 22gDVB, reaction 2h after drip 5g acrylic acid, continue stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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 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, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed than 9:1 by Solute mass, be mixed with the solution that concentration is 1%, under 40W, 30KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 10min in mixed solution stainless steel cloth immersion step (6) 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 150 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with 50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is 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 obtained in DataphysicsOCA40Micro type surface contact angle tester step (1) empty silk screen and step (7) in atmosphere, prove that this nethike embrane has super hydrophilicity.
(7) water red ink is dyeed, with trimethylbenzene 1:1 mixing and stirring by volume, oil-water mixture is poured in this film, red water permeates downwards continually, and trimethylbenzene is blocked on film all the time, on even most telolemma, redness does not all remain, thus reaches oil-water separation.
Embodiment 6
(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) 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 DEG C gradually, then by 0.2g sodium peroxydisulfate, the mixture of 0.225g methacrylic acid and 2.2g styrene composition is disposable to add, and 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, 3g mercaptoethanol, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 50g deionized water, 3gDNS ?458,80g styrene, 19g crosslinking agent DVB, reaction 2h after drip 2g methacrylic acid, continue stir and be incubated 1h, rear dropping nertralizer triethylamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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 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, 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%, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 10min in mixed solution stainless steel cloth immersion step (6) 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 150 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with 50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is 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 obtained in DataphysicsOCA40Micro type surface contact angle tester step (1) empty silk screen and step (7) in atmosphere, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, 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 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
(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) 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 DEG C gradually, then by 0.2g sodium peroxydisulfate, the mixture of 0.225g methacrylic acid and 2.2g styrene composition is disposable to add, and 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, 3g mercaptoethanol, and agitating heating is warming up to 85 DEG C, 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 drip remaining in 225min, 1h add 50g deionized water, 3gDNS ?458,80g styrene, 19g crosslinking agent DVB, reaction 2h after drip 2g methacrylic acid, continue stir and be incubated 1h, rear dropping nertralizer N, N dimethylethanolamine 100% neutralizes;
With Hitachi, Ltd S ?the form of emulsion particle prepared of 3700N type SEM, FEI Co. Quanta200 type ultrahigh resolution field emission scanning electron microscope and NovaNanoSEM430 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 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, similar to Fig. 3;
(6) the emulsion particle solution in step (4) and step (5) gained Ludox are mixed than 1:1 by Solute mass, add water and be mixed with the solution that concentration is 99%, under 500W, 40KHz, ultrasonic disperse 10min is to ensure to be uniformly dispersed;
(7) 5min in mixed solution terylene silk net immersion step (6) 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 60min in the vacuum drying oven of 150 DEG C.
With Hitachi, Ltd S ?the surface topography of 3700N type sem observation nethike embrane and relative dimensions.300 order copper mesh are coated with 50 μm of thick hydrophilic polymer clads doped with inorganic nano-particle; In silk screen interval, there is the micropore in 40 μm of apertures, be all the projection of the thick just structure of micro-nano around micropore simultaneously; Be that the SEM 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 μm, simultaneously on micron ball and there is 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 obtained in DataphysicsOCA40Micro type surface contact angle tester step (1) empty silk screen and step (7) in atmosphere, prove that this nethike embrane has super hydrophilicity.
(8) water red ink is dyeed, with hexadecane 4:1 mixing and stirring by volume, add 0.2g neopelex, magnetic agitation 15min makes O/W emulsion, emulsion poured in this film, 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 (9)
1. a super preparation method that the is hydrophilic and oil-water separation mesh film of 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 ?the mixing of 0.0252 part of emulsifier for mixing, be warming up to 85 ?90 DEG C, 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 DEG C, slowly add in 1h 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 liquor of 1.056 parts of initators composition, 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) adopt Rong Jiao ?gel method, with tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide for 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 20 ?, 80 DEG C of waters bath with thermostatic control, stirring, 5 ?after 10min, drip catalyst, be incubated 4 ?5h, namely 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 polymeric emulsion particle microballoon and step 5) in Nano sol in mass ratio 1:9 ?the proportions of 9:1 become concentration be 1 ?99% mixed solution, ultrasonic disperse is even;
7) will the silk screen that obtain in step (1) immerse step 6) in mixed solution in, soak 5 ?it is vertically lifted after 20min, or adopt high-pressure spray gun direct spraying, by soak or silk screen after spraying hang in constant-temperature vacuum baking oven maintain the temperature at 100 ?200 DEG C of oven dry; Must super oil-water separation mesh film that is 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. super preparation method that the is hydrophilic and oil-water separation mesh film of super oleophobic under water according to claim 1, it is characterized in that: described He ?shell polymeric emulsion particle microballoon based on styrene, domain size distribution 100 ?between 500nm, microsphere surface is rich in carboxylic salts; Nano particle diameter in described Nano sol control 10 ?500nm, nano particle mass content be 20 ?35%.
3. super preparation method that the is hydrophilic and oil-water separation mesh film of super oleophobic under water according to claim 1, 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 fiber fabric web.
4. super preparation method that the is hydrophilic and oil-water separation mesh film of super oleophobic under water according to claim 1, is characterized in that: the supersonic frequency of described ultrasonic cleaning be 20 ?40KHz, power bracket be 100 ?150W; The supersonic frequency of described ultrasonic disperse be 20 ?40KHz, power bracket be 300 ?500W.
5. super preparation method that the is hydrophilic and oil-water separation mesh film of 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. super preparation method that the is hydrophilic and oil-water separation mesh film of super oleophobic under water according to claim 1, is characterized in that: the speed of described dropping catalyst be 1 ?10ml/min.
7. super preparation method that the is hydrophilic and oil-water separation mesh film of super oleophobic under water according to claim 1, is characterized in that: described mixed liquor adds 50% in 75min, remainingly drips in 225min.
8. super oil-water separation mesh film that is hydrophilic and super oleophobic under water, is characterized in that, its by claim 1 ?preparation method described in 7 any one obtain; Described oil-water separation mesh film be 100 ?300 object screen of fabric are coated with the hydrophilic polymer clad doped with inorganic nano-particle of micron thickness, 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 micron thickness be 11 ?50 μm; The spherical protuberances particle diameter of micro-meter scale be 1 ?50 μm; The particle diameter of the spherical protuberances of nanoscale be 10 ?900nm; 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.
9. the application of super oil-water separation mesh film that is hydrophilic and super oleophobic under water according to claim 8 in the separation of oil water mixture and the process of oil-polluted water.
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