CN105664897A - Method for preparing magnetic porous microsphere adsorbing material by utilizing O/W/O double emulsion template - Google Patents
Method for preparing magnetic porous microsphere adsorbing material by utilizing O/W/O double emulsion template Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a method for preparing a magnetic porous microsphere adsorbing material by utilizing an oil-water-oil double emulsion template. The method comprises the steps of taking a natural polymer hydroxy propyl cellulose as a matrix, a polymerizable functional monomer as a modifier, water as a continuous phase, an organic solvent as an organic dispersed phase, modified Fe3O4 magnetic particles as an emulsion stabilizer and a nonionic surfactant as an emulsion co-stabilizer, stirring in the presence of an initiator and a cross-linking agent, and obtaining a Pickering emulsion; adding the Pickering-emulsion into the organic solvent containing a surfactant for further emulsification, and then obtaining the magnetic porous microsphere adsorbing material through a polymerization reaction, wherein the diameter of microspheres is within the range of 5 to 20mum. The spherical structure is regular, the surface and the interior of each microsphere contain abundant pore structures and functional groups, the adsorption rate and the adsorption capacity to heavy metal can be remarkably improved, and the magnetic porous microsphere adsorbing material has very good properties of magnetic separation and reuse.
Description
Technical field
The preparation method that the present invention relates to a kind of magnetic porous microspheres adsorbing material, particularly relates to the method that the double; two emulsion template of a kind of O/W/O of utilization prepares magnetic porous microspheres adsorbing material, belongs to technical field of polymer materials.
Background technology
Along with industrialization and urbanization process, water pollution problems particularly Water Basin Water Pollution has become the main Environmental Problems of restriction socio-economic development. According to " Heavy Metal Pollution " 12 " planning ", by 2015, China will set up fairly perfect Heavy Metal Pollution system. Along with the progressively expansion of this planning, the emission request of industrial and mining establishment is also more and more stricter. Simultaneously to how the heavy metal in polluted-water repairs the urgent task having become current effectively. Therefore, explore the new approaches solving Water Basin Water Pollution problem and new method has important theory and realistic meaning for the sustainable use of basin water resources, socioeconomic sustainable development.
The controlling way of heavy metal pollution of water body mainly includes two aspects, it may be assumed that Sources controlling and pollution amelioration. And repairing and treating generally adopts two Basic Ways: one is the bioavailability reducing heavy metal and the transfer ability in water body; Two is heavy metal thoroughly removed from polluted water body. Wherein heavy metal thoroughly being removed from polluted water body is a kind of method taken stopgap measures and effect a permanent cure, but requires that adsorbing material not only has the ability of efficient absorption heavy metal in water, to be prone to simultaneously from water body and separate. In recent years, porous material advantage in absorption highlights gradually. The existence of pore structure is not only advantageous to the abundant exposure of adsorption group, and accelerates the heavy metal ion effect of mass transmitting at absorbent interior, thus realize the rate of adsorption and adsorption capacity promotes simultaneously.
Emulsion template method is used for preparing porous material absorption agent, and preparation process is simple, efficient. And replace surfactant stable emulsion not only can improve adsorbing material intensity with particle, and porous adsorbing material can be given further with new performance, such as magnetic, in order to separate after absorption.
O/W/O type emulsion is to obtain trickle oil-in-water (O/W) primary emulsion by an emulsifying, then adds it to another oil phase and carry out two step emulsion processes of reemulsification and prepare.Due to O/W/O type stability of emulsion, thus it it is an extraordinary support template. At present, there is not been reported to utilize the double; two emulsion template of O/W/O to prepare the method for porous microsphere.
Summary of the invention
It is an object of the invention to utilize the feature of the double; two emulsion template of O/W/O, it is provided that the method that the double; two emulsion template of a kind of O/W/O of utilization prepares magnetic porous microspheres adsorbing material, to improve its absorption property and to separate repetition utility.
One, the preparation of magnetic porous microspheres adsorbing material
The present invention prepares the method for magnetic porous microspheres adsorbing material, is with natural polymer hydroxypropyl cellulose for matrix, and polymerizable functional monomer is dressing agent, and with water for continuous phase, organic solvent is discontinuous organic phase, MODIFIED Fe3O4Magnetic particle is emulsion stabilizer, and nonionic surfactant is emulsion co-stabilizer, and under initiator, cross-linking agent exist, stirring prepares Pickering-emulsion; Pickering-emulsion is joined further emulsifying in the organic solvent containing surfactant again, then passes through polyreaction, prepare magnetic porous microspheres adsorbing material.
Its concrete preparation technology is: be under agitation well-dispersed in continuous phase water by hydroxypropyl cellulose, polymerisable function monomer, cross-linking agent, emulsion stabilizer, emulsion co-stabilizer, initiator, discontinuous organic phase is added again in aqueous phase, under 500 ~ 2000rpm mixing speed, stir 5min ~ 240min, obtain Pickering-emulsion; Then Pickering-emulsion is joined in the organic solvent containing surfactant, under 1000 ~ 12000rpm mixing speed, stir 1 ~ 10min; Then at 30 ~ 80 DEG C, it is polymerized 2-24h; Products therefrom acetone surname extraction 12 ~ 48h, then through industrial alcohol dehydration 12-48h, vacuum drying, obtains magnetic porous spherical gel adsorbing material.
Described polymerisable function monomer be acrylamide,NAt least one in-N-isopropylacrylamide, maleic acid, acrylic acid, methacrylic acid, methyl methacrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, butyl acrylate, styrene, 2-acrylamide-2-methyl-propanesulfonic acid, itaconic acid.
The mass ratio of described hydroxypropyl cellulose and polymerisable function monomer is 1:2 ~ 1:8.
Described cross-linking agent be ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, triallyl isocyanate,N,N’One in-methylene-bisacrylamide; The consumption of cross-linking agent is the 1 ~ 20% of hydroxypropyl cellulose and polymerisable function monomer gross mass.
Described initiator is the one in potassium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile, benzoyl peroxide; The consumption of initiator is the 0.2 ~ 5% of hydroxypropyl cellulose and polymerisable function monomer gross mass.
Organic solvent as discontinuous organic phase is at least one in toluene, benzene, xylol, liquid paraffin, normal hexane, normal heptane, normal octane, n-decane, Oleum Terebinthinae, carbon tetrachloride; The volume ratio of continuous phase water and discontinuous organic phase is 1:2.3 ~ 1:5.6.
Nonionic surfactant as emulsion co-stabilizer is at least one in fatty alcohol-polyoxyethylene ether, alkylphenol polyethylene oxide ether, fatty acid polyglycol cyclic ethylene alkane ester, Pluronic F-127 alkylamine, polyxyethylated acyl hydramine, polyoxyethylene polyoxypropylene block copolymer, fatty acid glyceride, sucrose fatty acid ester, Span, sorbitan fatty acid ester; The consumption of emulsion co-stabilizer is the 0.5 ~ 5% of discontinuous organic phase volume.
Described Pickering-emulsion joins in the organic solvent containing surfactant in the technique of further emulsifying, and organic solvent is at least one in toluene, benzene, xylol, liquid paraffin, normal hexane, normal heptane, normal octane, n-decane, Oleum Terebinthinae, carbon tetrachloride, Polyethylene Glycol, glycerol; Surfactant is at least one in fat polyoxyethylenated alcohol, alkylphenol polyethylene oxide ether, fatty acid polyglycol cyclic ethylene alkane ester, Pluronic F-127 alkylamine, polyxyethylated acyl hydramine, polyoxyethylene polyoxypropylene block copolymer, fatty acid glyceride, sucrose fatty acid ester, Span and sorbitan fatty acid ester; The consumption of surfactant is the 5.0 ~ 20.0% of organic solvent quality.
Described MODIFIED Fe3O4Magnetic particle, is by Fe3O4Magnetic particle and modifying agent are mixed in ethanol, and under 60 DEG C of conditions, 500rpm stirs 12h, then obtains with after ethanol and water washing; The modifying agent adopted is at least one in oleic acid, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, (3-aminopropyl) trimethoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane, tetraethyl orthosilicate, aminopropyltriethoxy diethoxy silane, 3-aminopropyl triethoxysilane; MODIFIED Fe3O4Magnetic particle consumption is the 0.2% ~ 4% of discontinuous organic phase volume.
Two, the structure of magnetic porous microspheres adsorbing material and morphology characterization
Below by characterization methods such as transmission electron microscope (TEM), X-ray diffraction (XRD), optical microscope and scanning electron microscopes (SEM), Pickering-emulsion prepared by the present invention and the structure and morphology of magnetic porous microspheres adsorbing material are analyzed.
1, TEM and XRD analysis
Fig. 1 is magnetic Fe prepared by the present invention3O4And modified magnetic Fe3O4TEM and XRD figure. From figure 1 it appears that magnetic Fe3O4Nanoparticle (Fig. 1 a) spherical structure is good, and particle diameter is about 110nm. After modification, surface reforming layer can be visible in detail, and particle radii significantly increase, and is about 170nm, and modified particle is homogeneous and favorable dispersibility.
To modified magnetic Fe3O4Particle carries out XRD analysis (Fig. 1 b) and finds afterwards, modified magnetic Fe3O4Characteristic absorption peak in (220), (311), (400), (511) and (440) yet suffers from, and illustrates modified not to Fe3O4Produce impact.
2, Optical microscopy
Fig. 2 is digital photograph (Fig. 2 a) and the optical microscope photograph (Fig. 2 b, c) of Pickering-emulsion prepared by the present invention. Pickering-emulsion prepared by the present invention is thickness coke yellow liquid, and stability of emulsion is good, stand at ambient temperature 3 months not stratified. Utilizing optical microscope to carry out observing discovery (Fig. 2 b), a large amount of oil-in-water droplets tightly " are crowded together ", modified magnetic Fe3O4It is scattered on oil-water interfaces uniformly, thus stabilized oil-in-water Pickering-emulsion well. After Pickering-emulsion emulsifying again to the third organic solvent, under an optical microscope can the double; two emulsion droplet (Fig. 2 c) of O/W/O visible in detail. Owing to double; two emulsion droplet light transmissions are poor, therefore it is that black is spherical under an optical microscope.
3, sem analysis
Fig. 3 is magnetic porous microspheres adsorbing material surface topography prepared by the present invention, and wherein, a and b is the external morphology of magnetic porous microspheres, and c is the inner porosity of magnetic porous microspheres. The spherical micro-sphere absorption material of magnetic that the present invention prepares has dark-brown spherical structure, and size is homogeneous, and microsphere diameter is about 15 μm (Fig. 3 a, b).It has been observed that have abundant pore passage structure (Fig. 3 c) inside magnetic porous microspheres adsorbing material under scanning electron microscope, this is beneficial to heavy metal ion and is rapidly introduced in internal gutter.
Fig. 4 is solvent swelling state in water and the Magneto separate process of magnetic porous microspheres adsorbing material prepared by the present invention. After this kind of magnetic porous microspheres adsorbing material is added to the water, it is only necessary to vibration or stirring can ensure its be uniformly dispersed (Fig. 4 a) gently. By external magnetic field, it is possible to quickly and conveniently adsorbent and adsorption liquid are separated, simplify greatly and facilitate the separation process (Fig. 4 b) after absorption. With observation by light microscope magnetic porous microspheres swelling process in aqueous phase it appeared that. Porous magnetic microsphere have in the dry state agglomeration exist (Fig. 4 c), but after being added to the water, its swelling process can complete in 10 seconds, and swelling bead single be present in water, do not reunite, favorable dispersibility (Fig. 4 d).
Three, the absorption of magnetic porous microspheres adsorbing material heavy metal and repeat performance
1, the absorption property of heavy metal lead and copper
Choose the Cu of 100mg/L and 400mg/L respectively2+And Pb2+Simulation heavy metal wastewater thereby 25mL, is added thereto to the spherical adsorbing material of magnetic of the present invention (initial amount is 0.8g/L), constant temperature oscillation difference adsorption time, it is seen that Cu in spectrophotometry supernatant2+And Pb2+Concentration. Fig. 5 is porous adsorbent Adsorption of Cu prepared by the present invention2+And Pb2+Adsorption capacity and rate of adsorption figure. As it is shown in figure 5, no matter be low concentration (100mg/L) or the heavy metal Cu of high concentration2+Solution, all can reach adsorption equilibrium in 3min; And for heavy metal Pb2+, absorption all can reach adsorption equilibrium at 5min. Illustrate no matter be low concentration or high concentration heavy metal ion, magnetic porous spherical adsorbing material prepared by the present invention can realize rapidly and efficiently Adsorption. And under outside the action of a magnetic field, the adsorbing material after adsorb can be separated quickly and easily from adsorption liquid, simplicity adsorption separation process greatly. Fig. 5 a shows, the spherical adsorbing material heavy metal Cu of magnetic prepared by the present invention2+And Pb2+Maximal absorptive capacity respectively 242.72mg/g and 468.49mg/g.
2, the repeat performance of heavy metal lead and copper
Choose the Cu of 200mg/L2+Pb with 300mg/L2+Simulation heavy metal wastewater thereby 25mL, is added thereto to the spherical absorption of magnetic of the present invention (initial amount 0.8g/L), constant temperature oscillation 1h, measures Cu in supernatant by visible spectrophotometry2+And Pb2+Concentration. After absorbent filtering, continue on for Cu after 0.5mol/LHCl solution desorption, 0.5mol/LNaOH regeneration of waste liquor2+And Pb2+Simulation heavy metal wastewater thereby absorption.
Fig. 6 is porous adsorbent Adsorption of Cu prepared by the present invention2+、Pb2+Repeat performance curve. As seen from Figure 6, no matter it is for Cu2+Or Pb2+, porous adsorbent, after 5 adsorption-desorption processes, remains in that good absorption property, and adsorption capacity reduction is respectively less than 10%.
In sum, magnetic porous microspheres adsorbing material prepared by the present invention, microsphere diameter is in the scope of 5 ~ 20 μm, spherical structure is regular, microsphere surface and inside are containing abundant pore passage structure and functional group, it is possible to significantly improve the rate of adsorption and the adsorption capacity of heavy metal, heavy metal Cu2+And Pb2+Maximal absorptive capacity respectively 242.72mg/g and 468.49mg/g, and there is extraordinary Magnetic Isolation and reusable performance.
Hinge structure of the present invention has the advantage that
1, adopt Pickering-emulsion technology, define stable oil-in-water type (O/W) emulsion, there is substantial amounts of one-level hole and second hole after polymerization, it is possible to achieve heavy metal Cu2+And Pb2+Rapidly and efficiently absorption;
2, adopt the double; two emulsion template technology of O/W/O, not only achieve the quick preparation of porous microsphere sorbent, shorten the manufacturing cycle of porous material, and porous adsorbing material is reduced in size to micron order, further speed up effect of mass transmitting;
3, adopt Pickering-emulsion technology, adopt MODIFIED Fe3O4Particle-stabilised emulsion, gives porous microsphere magnetic, it is simple to the separation of adsorbent and recovery in adsorption process;
4, magnetic porous spherical adsorbing material prepared by the present invention has extraordinary reusable performance, effectively reduces the cost of heavy metal water body treating;
5, the organic solvent used in preparation process of the present invention can be reused after suitably processing, and effectively reduces preparation cost.
Accompanying drawing explanation
Fig. 1 is magnetic Fe prepared by the present invention3O4Transmission electron microscope (TEM) after before modified and X-ray diffraction (XRD) figure.
Fig. 2 is the optical microscope of the double; two emulsion of the digital photograph of Pickering-High Internal Phase Emulsion prepared by the present invention and optical microscope and O/W/O.
Fig. 3 is the scanning electron microscope (SEM) photograph of magnetic porous spherical adsorbing material prepared by the present invention.
Fig. 4 is the optical microscope of solvent swelling state in water and the Magneto separate process photo of the magnetic porous microspheres adsorbing material prepared of the present invention.
Fig. 5 is porous adsorbent Adsorption of Cu prepared by the present invention2+And Pb2+Adsorption capacity and rate of adsorption figure.
Fig. 6 is porous adsorbent Adsorption of Cu prepared by the present invention2+And Pb2+Repeat performance curve.
Detailed description of the invention
Below in conjunction with embodiment, the preparation of the magnetic porous spherical adsorbing material of the present invention is described further.
Embodiment 1
By 0.1g hydroxypropyl cellulose, 2.0g hydroxyethyl methylacrylate, 1.5g itaconic acid, 3.0g ethylene glycol dimethacrylate, 0.2g MODIFIED Fe under 200rpm stirs3O4, the polyxyethylated acyl alcamines surfactant-dispersed of 1.0g is in 5mL water; After treating that each component is dissolved, in mixed liquor, add toluene 10mL stir 4h, add initiator benzoyl peroxide 0.5g, stir 2min at 100 rpm, obtain Pickering-emulsion;
Pickering-emulsion joins 25mL xylol (containing polyxyethylated acyl alcamines surfactant 2.5g), dispersed with stirring 1min under 8000rpm; It is then charged into test tube and is polymerized 4h in 70 DEG C; After resulting polymers normal hexane surname extraction 48h, vacuum drying, obtain magnetic porous microspheres adsorbing material.
This adsorbing material heavy metal Cu2+And Pb2+Remove adsorbance respectively 125mg/g and 203mg/g.
Embodiment 2
By 0.6g hydroxypropyl cellulose, 1.5g2-acrylamide-2-methyl-propanesulfonic acid, 2.0g maleic acid, 2.0g under 500rpm stirsN,N’-methylene-bisacrylamide, 0.1g MODIFIED Fe3O4, 1.0g alkylphenol polyethylene oxide ether surfactant is scattered in 3mL water; After treating that each component is dissolved, in mixed liquor, add hexamethylene 6mL stir 2h, add initiator ammonium persulfate 0.2g, stir 1min at 100 rpm, obtain Pickering-emulsion;
Pickering-emulsion is joined 9mL liquid paraffin (containing polyoxyethylene polyoxypropylene block copolymer class surfactant 0.45g), dispersed with stirring 2min at 3,000 rpm, is then charged into test tube and is polymerized 12h in 40 DEG C;Resulting polymers acetone surname extraction 48h, vacuum drying, obtain magnetic porous microspheres adsorbing material.
This adsorbing material heavy metal Cu2+And Pb2+Remove adsorbance respectively 153mg/g and 388mg/g.
Embodiment 3
By 0.3g hydroxypropyl cellulose, 2.0g methacrylic acid, 1.0g acrylic acid, 0.3g MODIFIED Fe under 800rpm stirs3O4, 0.15g fatty alcohol polyethenoxy ether class surfactant-dispersed is in 4mL water; After treating that each component is dissolved, in mixed liquor, add xylol 6mL stir 2h, add initiator azodiisobutyronitrile 0.3g, stir 4min at 100 rpm, obtain Pickering-emulsion;
Pickering-emulsion is joined (fatty acids polycyclic ethylene alkane esters surface active agent 6g) in 30mL hexamethylene, then dispersed with stirring 2min under 5000rpm; It is then charged into test tube and is polymerized 4h in 70 DEG C; Resulting polymers normal hexane surname extraction 24h, after industrial alcohol processed, obtains magnetic porous microspheres adsorbing material.
This adsorbing material heavy metal Cu2+And Pb2+Remove adsorbance respectively 282mg/g and 378mg/g.
Embodiment 4
By 1.0g hydroxypropyl cellulose, 2.0g under 1800rpm stirsN-N-isopropylacrylamide, 1.0g methacrylic acid, 2.5gN,N’-methylene-bisacrylamide, 1.2g MODIFIED Fe3O4, 3.0g polyoxyethylene polyoxypropylene block copolymer class surfactant-dispersed is in 5mL water; After treating that each component is dissolved, in mixed liquor, add normal hexane 10mL stir 1h, add initiator potassium persulfate 0.3g, stir 2min at 100rpm, obtain Pickering-emulsion;
Pickering-emulsion is joined (containing sorbitan fatty acid ester class surfactant 6g) in 30mL normal hexane, dispersed with stirring 1min under 12000rpm, it is then charged into test tube and is polymerized 12h in 40 DEG C; Resulting polymers, through acetone surname extraction 24h, vacuum drying, obtains magnetic porous microspheres adsorbing material.
This adsorbing material heavy metal Cu2+And Pb2+Remove adsorbance respectively 179mg/g and 363mg/g.
Embodiment 5
By 0.8g hydroxypropyl cellulose, 2.0g itaconic acid, 2.5g-acrylamide-2-methyl-propanesulfonic acid, 1.5g ethylene glycol dimethacrylate, 0.6g MODIFIED Fe under 1200rpm stirs3O4, 2.0g polyoxyethylene polyoxypropylene block copolymer class surfactant-dispersed is in 3mL water; After treating that each component is dissolved, in mixed liquor, add xylol 12mL stir 4h, add initiator ammonium persulfate 0.5g, stir 3min at 100 rpm, obtain Pickering-emulsion;
Pickering-emulsion is joined (containing sorbitan fatty acid ester class surfactant 3g) in 30mL liquid paraffin, dispersed with stirring 3min under 6000rpm, it is then charged into test tube and is polymerized 24h in 50 DEG C; Resulting polymers, through normal hexane surname extraction 48h, vacuum drying, obtains magnetic porous microspheres adsorbing material.
This adsorbing material heavy metal Cu2+And Pb2+Remove adsorbance respectively 212mg/g and 268mg/g.
In the various embodiments described above, MODIFIED Fe3O4Magnetic particle is obtained by following technique: by 0.5gFe3O4After disperseing 2h in 100mL ethanol under 500rpm stirs, add 2mL modifying agent, continue stirring 12h at 60 DEG C; After products therefrom second alcohol and water respectively washes 3 times, dry for 60 DEG C. The modifying agent adopted is at least one in oleic acid, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, (3-aminopropyl) trimethoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane, tetraethyl orthosilicate, aminopropyltriethoxy diethoxy silane, 3-aminopropyl triethoxysilane.
Claims (10)
1. utilizing the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material, be with natural polymer hydroxypropyl cellulose for matrix, polymerizable functional monomer is dressing agent, and with water for continuous phase, organic solvent is discontinuous organic phase, MODIFIED Fe3O4Magnetic particle is emulsion stabilizer, and nonionic surfactant is emulsion co-stabilizer, and under initiator, cross-linking agent exist, stirring prepares Pickering-emulsion; Pickering-emulsion is joined further emulsifying in the organic solvent containing surfactant again, then passes through polyreaction, prepare magnetic porous microspheres adsorbing material.
2. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1, it is characterized in that: under agitation hydroxypropyl cellulose, polymerisable function monomer, cross-linking agent, emulsion stabilizer, emulsion co-stabilizer, initiator are well-dispersed in continuous phase water, discontinuous organic phase is added again in aqueous phase, under 500 ~ 2000rpm mixing speed, stir 5min ~ 240min, obtain Pickering-emulsion; Then Pickering-emulsion is joined in the organic solvent containing surfactant, under 1000 ~ 12000rpm mixing speed, stir 1 ~ 10min; Then at 30 ~ 80 DEG C, it is polymerized 2-24h; Products therefrom acetone surname extraction 12 ~ 48h, then through industrial alcohol dehydration 12-48h, vacuum drying, obtains magnetic porous microspheres adsorbing material.
3. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: described polymerisable function monomer be acrylamide,NAt least one in-N-isopropylacrylamide, maleic acid, acrylic acid, methacrylic acid, methyl methacrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, butyl acrylate, styrene, 2-acrylamide-2-methyl-propanesulfonic acid, itaconic acid.
4. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: the mass ratio of described hydroxypropyl cellulose and polymerisable function monomer is 1:2 ~ 1:8.
5. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: described cross-linking agent be ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, triallyl isocyanate,N,N’One in-methylene-bisacrylamide; The consumption of cross-linking agent is the 1 ~ 20% of hydroxypropyl cellulose and polymerisable function monomer gross mass.
6. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: described initiator is the one in potassium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile, benzoyl peroxide; The consumption of initiator is the 0.2 ~ 5% of hydroxypropyl cellulose and polymerisable function monomer gross mass.
7. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: the organic solvent as discontinuous organic phase is at least one in toluene, benzene, xylol, liquid paraffin, normal hexane, normal heptane, normal octane, n-decane, Oleum Terebinthinae, carbon tetrachloride; The volume ratio of continuous phase water and discontinuous organic phase is 1:2.3 ~ 1:5.6.
8. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: the nonionic surfactant as emulsion co-stabilizer is at least one in fatty alcohol-polyoxyethylene ether, alkylphenol polyethylene oxide ether, fatty acid polyglycol cyclic ethylene alkane ester, Pluronic F-127 alkylamine, polyxyethylated acyl hydramine, polyoxyethylene polyoxypropylene block copolymer, fatty acid glyceride, sucrose fatty acid ester, Span, sorbitan fatty acid ester;The consumption of emulsion co-stabilizer is the 0.5 ~ 5% of discontinuous organic phase volume.
9. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterized in that: Pickering-emulsion being joined in the organic solvent containing surfactant in the technique of further emulsifying, organic solvent is at least one in toluene, benzene, xylol, liquid paraffin, normal hexane, normal heptane, normal octane, n-decane, Oleum Terebinthinae, carbon tetrachloride, Polyethylene Glycol, glycerol; Surfactant is at least one in fat polyoxyethylenated alcohol, alkylphenol polyethylene oxide ether, fatty acid polyglycol cyclic ethylene alkane ester, Pluronic F-127 alkylamine, polyxyethylated acyl hydramine, polyoxyethylene polyoxypropylene block copolymer, fatty acid glyceride, sucrose fatty acid ester, Span and sorbitan fatty acid ester; The consumption of surfactant is the 5.0 ~ 20.0% of organic solvent quality.
10. utilize the method that the double; two emulsion template of O/W/O prepares magnetic porous microspheres adsorbing material as claimed in claim 1 or 2, it is characterised in that: described MODIFIED Fe3O4Magnetic particle, is by Fe3O4Magnetic particle and modifying agent are mixed in ethanol, and under 60 DEG C of conditions, 500rpm stirs 12h, obtains after then repeatedly washing with second alcohol and water; The modifying agent adopted is at least one in oleic acid, sodium lauryl sulphate, dodecylbenzene sodium sulfonate, (3-aminopropyl) trimethoxy silane, 3-(methacryloxypropyl) propyl trimethoxy silicane, tetraethyl orthosilicate, aminopropyltriethoxy diethoxy silane, 3-aminopropyl triethoxysilane; MODIFIED Fe3O4Magnetic particle consumption is the 0.2% ~ 4% of discontinuous organic phase volume.
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