CN104485191A - Magnetic hollow nanometer ball and preparation method thereof - Google Patents
Magnetic hollow nanometer ball and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnetic hollow nanometer ball and a preparation method of the magnetic hollow nanometer ball. A shell layer of the magnetic hollow nanometer ball is silicon-containing polymer containing magnetic particles. The silicon-contained polymer comprises products formed by polymerizing tetramethoxysilane containing double-bond function groups or ethyl silicate containing double-bond function groups. The magnetic particles comprise iron oxides and/or iron oxides doped with other metal. The grain size of the magnetic hollow nanometer ball ranges from 50 nm to 1 micron, and the thickness of the shell layer ranges from 20 nm to 500 nm.
Description
Technical field
The invention belongs to inorganic nano material and manufacture field, be specifically related to a kind of magnetic hollow nanosphere and preparation method thereof.
Background technology
Magnetic hollow nanosphere material is a kind of nano material with special construction, and its yardstick is in nanometer in micrometer range, and particle is hollow-core construction.Material not only has the special nature (comprising Magneto separate, superparamagnetic character and magnetic resonance imaging imaging character) of magnetic material, and the structure of hollow makes it have the features such as higher specific area, less composition density, larger internal cavities and Surface Permeability are good simultaneously.Therefore, in fields such as drug delivery, diagnosis of disease, biochip manufacture, separated from contaminants, catalysis protection and Mass Spectrometer Method, all there is important application prospect.
In recent years, the synthesis technique of hollow magnetic ball, structure regulating and application study have obtained and have paid close attention to widely both at home and abroad.Australian Scientists Caruso etc. by polymer template layer by layer coated magnetic nano particle obtain composite magnetic microballoon, then obtain magnetic hollow microsphere (Chem.Mater., 2001,13,109-116) through oversintering.The people such as domestic Tang adopt the organic micro-spheres of different-grain diameter size to be template, by controlling the hydrolytic polymerization degree of divalent iron salt solution at microsphere surface, obtain the complex microsphere of different shell thickness, and synthesis (the J.Colloid InterfaceSci. of magnetic hollow microsphere is realized further by calcining, 2005,281,432 – 436).The people such as Korea S Hwang are by the Fe of surface negative charge modification
3o
4nano particle and the stronger charge forces of cation template, in hollow mesoporous silicon oxide Hydrothermal Synthesis process, magnetic-particle is incorporated in mesopore orbit in situ, template is removed again through calcining, obtain the mesoporous silica hollow ball (Eur.J.Inorg.Chem. of magnetic, 2012,3379 – 3383).
But the approach mainly form technology of current synthesizing magnetic hollow nanospheres, needs through being blended into the multiple operations such as template removal from hard or soft template synthesis, nucleocapsid structure.Complexity and the preparation difficulty of its synthesis technique are high, the size heterogeneity of prepared material and bad dispersibility.In addition, need a large amount of organic solvent or high-temperature calcination in template removal processes, its environmental pollution is large.Above some questions limits suitability for industrialized production and marketing application.For these problems, develop that a kind of technique is simple, the preparation method of mild condition, morphology controllable, good dispersion and eco-friendly magnetic hollow nano particle has important Research Significance and promotional value.
Summary of the invention
The present invention is intended to expand the kind of existing magnetic hollow nanosphere and promotes its performance parameter, the invention provides a kind of magnetic hollow nanosphere and preparation method thereof.
The invention provides a kind of magnetic hollow nanosphere, the shell of described magnetic hollow nanosphere is the silicon-containing polymer containing magnetic-particle, wherein, silicon-containing polymer comprises the product be polymerized by the methoxy silane containing double bond functional group or Ethoxysilane, magnetic-particle comprises ferriferous oxide and/or the ferriferous oxide of other metal that adulterates, described magnetic hollow nanosphere particle diameter be 50nm-1 μm, shell thickness is 20nm-500nm.
Preferably, the mass percent that magnetic-particle accounts for shell is 0.02%-90.9%, and the particle diameter of magnetic-particle is 1nm-20nm.
Preferably, magnetic hollow nanosphere particle diameter be 50nm-150nm, shell thickness is 40nm-500nm, and shell has nano-pore, and aperture is 0.1nm-10nm, and the aperture of preferred nano-pore is 1nm-2nm.
Preferably, magnetic-particle comprises at least one in tri-iron tetroxide, di-iron trioxide, four oxygen two cobalt ferrites, and the particle diameter of magnetic-particle is 3nm-10nm.
In addition, present invention also offers a kind of preparation method of above-mentioned magnetic hollow nanosphere, comprising:
1) magnetic-particle is added in the aqueous solution of dispersion stabilizer, first dispersed, be then separated the dispersion stabilizer removed and do not adsorb magnetic-particle, obtain the suspension being dispersed with magnetic-particle;
2) by step 1) suspension, silane coupler and the volatile organic solvent prepared, be added to the water, stir and form emulsion;
3) by step 2) after the heating of the emulsion prepared, add polymerization initiator wherein for initiated polymerization;
4) treat step 3) in after solution reaction, be separated, drying obtain described magnetic hollow nanosphere.
Preferably, step 1) in, the mass ratio of magnetic-particle and dispersion stabilizer is (0.1-10): 1, and in suspension, the concentration of magnetic-particle is 0.1-50mg/mL;
Dispersion stabilizer comprises at least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, tetramethyl ammonium chloride, etamon chloride, 4-propyl ammonium chloride, 4 bromide, tetraethylammonium bromide, 4-propyl bromide, TBAB.
Preferably, step 1) in, dispersedly comprise ultrasonic disperse, separation method comprises centrifugal or Magnetic Isolation.
Preferably, step 2) in, silane coupler comprises methoxy silane containing double bond functional group and/or Ethoxysilane, and volatile solvent comprises at least one in isobutyl acetate, butyl acetate, isoamyl acetate, pentyl acetate, hexyl acetate;
Suspension: silane coupler: the usage ratio of easy volatile solvent is 1mL:(5mg-500mg): (0.01mL-6mL), preferred 1mL:(5mg-500mg): (0.01mL-1mL); In emulsion, the concentration of silane coupler is 1mg/mL-1000mg/mL.
Preferably, step 3) in, polymerization initiator: the consumption mol ratio of silane coupler is (0.1-10): 1, and polymerization initiator comprises persulfate, hydrogen peroxide and/or water-soluble azo initiator.
Preferably, step 2) in, mixing time is greater than 0.5h, preferred 24h-48h;
Step 3) in, emulsion heating-up temperature is higher than 50 DEG C, and preferably 60 DEG C-70 DEG C, polymerization reaction time is greater than 0.1 hour, preferably 12 hours-24 hours;
Step 4) in, baking temperature higher than 30 DEG C, preferably 100 DEG C-150 DEG C.
Beneficial effect of the present invention:
Magnetic hollow nanosphere of the present invention is because have silicone hydroxyl, therefore nanosphere finishing silane coupler (including but not limited to the silane coupler etc. containing amino, sulfydryl, phenyl ring, double bond and carboxyl), the compound with the multiple material comprising polymer, protein, other functionalized nanoparticles, dispersant and biological coating can be realized further;
Magnetic hollow nanosphere size tunable of the present invention built in below 100nm, simultaneously material biological safety and compatibility good, drugloading rate is high, and therefore this material can improve medicine in the enrichment of tumor region and result for the treatment of effectively as nano-medicament carrier; Said structure feature makes magnetic hollow nanosphere be applicable to being applied to the multiple fields such as drug delivery, medical diagnosis on disease, ultrasonic therapy, biochip, separated from contaminants, catalyst protection, nano-reactor and Mass Spectrometer Method.Meanwhile, technology of preparing output of the present invention is high, and preparation technology is simple and easy to, repeatability strong, is therefore applicable to industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 shows the low power images of transmissive electron microscope of the magnetic hollow nanosphere of embodiment 1;
Fig. 2 shows the high power images of transmissive electron microscope of the magnetic hollow nanosphere of embodiment 1;
Fig. 3 shows the scanning electron microscope image of the magnetic hollow nanosphere of embodiment 1;
Fig. 4 shows the transmission electron microscope picture of magnetic hollow nanosphere in embodiment 2;
Fig. 5 shows the transmission electron microscope picture of magnetic hollow nanosphere in embodiment 3;
Fig. 6 shows the transmission electron microscope picture of magnetic solid nanospheres in comparative example 1;
Fig. 7 shows the nitrogen adsorption desorption curve of the magnetic hollow nanosphere of embodiment 1 and corresponding specific surface area data.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
The present invention is directed to magnetic hollow nanosphere synthesis technique in prior art loaded down with trivial details, the technical problems such as scantling heterogeneity and bad dispersibility, object is to provide a kind of novel magnetic hollow nanosphere.
The invention discloses a kind of magnetic hollow nanosphere and preparation method thereof, the shell of magnetic hollow nanosphere of the present invention is the nano-pore structure of siliceous polymer composition, and super-small magnetic-particle is with the shell outer surface of embedded formal distribution at ball.Described magnetic hollow nanosphere size tunable; thermodynamics is high and structural stability is high; there is magnetic, can be used for the fields such as drug delivery, medical diagnosis on disease, ultrasonic therapy, biochip, separation, catalyst protection and Mass Spectrometer Method, have broad application prospects.The preparation condition of material is gentle, simple, pollution-free and output is high, is applicable to industrialization large-scale production.
Described magnetic hollow nanosphere has cavity structure, and shell forms primarily of silicon-containing polymer, and super-small magnetic-particle with the outer surface of embedded formal distribution at spherical shell, and has partial denudation outside shell.
The particle diameter of described particle is 50nm-1 μm, preferred 50nm-150nm, more preferably 50nm-80nm; Described shell thickness is 40nm-500nm, preferred 40nm-100nm, more preferably 20nm-40nm.
Described shell has nano pore, and aperture is about 0.1nm-10nm, preferred 1nm-2nm.
Super-small magnetic-particle consists of the oxide of tri-iron tetroxide, di-iron trioxide, four oxygen two cobalt ferrites and other metal-doped iron, preferred ferroferric oxide nano granules.
The particle diameter of super-small magnetic-particle is about 1nm-20nm, preferred 3nm-10nm.
Described hollow-core construction is by the Material synthesis comprising super-small magnetic-particle, silane coupler and effumability solvent.Described silicon-containing polymer includes but are not limited to the product be polymerized by the methoxy silane containing double bond functional group or Ethoxysilane, preferably containing the methoxy silane of double bond functional group, more preferably 3-(methacryloxypropyl) propyl trimethoxy silicane.
On material preparation process, the present invention achieves the preparation of the composite nano materials with hollow porous structure and magnetic property performance mainly through emulsification and polymerization two steps.In preparation process, use a kind of volatile solvent (as isoamyl acetate) to be template, in dry run, directly remove template, mild condition, preparation technology are simple to operation.Need not the use of harmful organic solvent or high-temperature calcination in building-up process.Therefore, another object of the present invention is to provide a kind of method preparing magnetic hollow nanosphere.
The invention provides a kind of method of above-mentioned magnetic hollow nanosphere, the method comprises the following steps:
Steps A) add super-small magnetic-particle containing finite concentration dispersion stabilizer the aqueous solution in disperse, be then separated the dispersion stabilizer removed and be not adsorbed on particle surface, be made into certain density super-small magnetic-particle suspension;
Step B) super-small magnetic-particle suspension, silane coupler and effumability solvent are added to the water, stir, form emulsion;
Step C) emulsion is heated, then add polymerization initiator, initiated polymerization;
Step D) be separated after obtain the magnetic hollow nanosphere that cavity contains easy volatile solvent, obtain magnetic hollow nanosphere powder after drying.
Step B) in emulsion synthesize adopt thermodynamically stable Pickering emulsion system.
Steps A) described in dispersion stabilizer include but are not limited to Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, tetramethyl ammonium chloride, etamon chloride, 4-propyl ammonium chloride, 4 bromide, tetraethylammonium bromide, 4-propyl bromide or TBAB, preferred Tetramethylammonium hydroxide;
Step B) described in described silane coupler include but are not limited to methoxy silane containing double bond functional group or Ethoxysilane, described easy volatile solvent includes but are not limited to isobutyl acetate, butyl acetate, isoamyl acetate, pentyl acetate or hexyl acetate;
Step C) described in polymerization initiator include but are not limited to persulfate, hydrogen peroxide or water-soluble azo initiator.
Steps A) described in super-small magnetic-particle and the mass ratio of dispersion stabilizer be 0.1-10:1, the concentration of described super-small magnetic-particle suspension is 0.1-50mg/mL;
Step B) described in super-small magnetic-particle suspension: silane coupler: the usage ratio of easy volatile solvent is 1mL:5mg-500mg:0.01mL-1mL, and in described emulsion, the concentration of silane coupler is 1mg/mL-1000mg/mL;
Step C) described in polymerization initiator: the consumption mol ratio of silane coupler is 0.1-10:1.
Steps A) described in temperature when disperseing be 10 DEG C-40 DEG C, preferably 20 DEG C-30 DEG C;
Step B) described in whipping temp be 10 DEG C-40 DEG C, preferably 20 DEG C-30 DEG C;
Step C) in emulsion heating-up temperature be higher than 50 DEG C, preferably 60 DEG C-70 DEG C;
Step D) in baking temperature higher than 30 DEG C, preferably 100 DEG C-150 DEG C.
Steps A) described in separation method be centrifugal or Magnetic Isolation, preferred Magnetic Isolation method;
Step B) described in mixing time be greater than 0.5h, preferred 24h-48h;
Step C) in polymerization reaction time be greater than 0.1h, preferred 12h-24h.
The present invention is in step D) in dry before the cavity that the obtains magnetic hollow nanosphere material that contains easy volatile solvent can treat diagnosis and treatment agent as a kind of novel high intensity focused ultrasound (HIFU), raising HIFU ablation effect.
Magnetic hollow nanosphere of the present invention has cavity structure, and its shell is the nano-pore structure of silicon polymer composition, can realize the absorption parcel of medicine, gene, protein and the guest species such as hazardous solvent and metal.Meanwhile, the super-small magnetic-particle that this nanosphere contains with the outer surface of embedded formal distribution at spherical shell, and has partial denudation outside shell.Its magnetic properties had, can be applicable to the purposes such as magnetic absorption separation and magnetic resonance imaging.Magnetic material and hollow porous organosilyl advantages characteristic are fused to that particle diameter is little by described magnetic hollow nanosphere effectively, the single nanosystems of uniform particle diameter, thermodynamics and structural stability excellence; in fields such as drug delivery, medical diagnosis on disease, ultrasonic therapy, biochip, separated from contaminants, catalyst protection and Mass Spectrometer Method, have broad application prospects.
Magnetic hollow nanosphere of the present invention is because have silicone hydroxyl, therefore nanosphere finishing silane coupler (including but not limited to the silane coupler etc. containing amino, sulfydryl, phenyl ring, double bond and carboxyl), the compound with the multiple material comprising polymer, protein, other functionalized nanoparticles, dispersant and biological coating can be realized further;
Magnetic hollow nanosphere size tunable of the present invention built in below 100nm, simultaneously material biological safety and compatibility good, drugloading rate is high, and therefore this material can improve medicine in the enrichment of tumor region and result for the treatment of effectively as nano-medicament carrier; Said structure feature makes magnetic hollow nanosphere be applicable to being applied to the multiple fields such as drug delivery, medical diagnosis on disease, ultrasonic therapy, biochip, separated from contaminants, catalyst protection, nano-reactor and Mass Spectrometer Method.Meanwhile, technology of preparing output of the present invention is high, and preparation technology is simple and easy to, repeatability strong, is therefore applicable to industrialization large-scale production.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
4nano granule suspension, 3-(methacryloxypropyl) propyl trimethoxy silicane of 30mg and the isoamyl acetate of 0.15mL join in 5mL water, stir preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 80nm, and average shell thickness is about 20nm, and topography uniformity is good.The mass percent that magnetic-particle accounts for shell is 14.3%.
Fig. 3 is the scanning electron microscope image of the magnetic hollow nanosphere of embodiment 1, can find Fe
3o
4nano particle is embedded in spherical shell surface, and has part to be exposed to outside spherical shell.
Fig. 7 is the nitrogen adsorption desorption curve of the magnetic hollow nanosphere of embodiment 1 and corresponding specific surface area data, and illustrative material has larger specific area and nano-pore structure.
Embodiment 2
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nanoparticle suspension solution.Then, 1mL Fe is got
3o
4nanoparticle suspension solution, 3-(methacryloxypropyl) propyl trimethoxy silicane of 5mg and the isoamyl acetate of 6mL join in 5mL water, stir preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 100nm, and average shell thickness is about 20nm, and topography uniformity is poor.The mass percent that magnetic-particle accounts for shell is 50%.
Embodiment 3
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
4nano granule suspension, 3-(methacryloxypropyl) propyl trimethoxy silicane of 5mg and the isoamyl acetate of 0.01mL join in 5mL water, stir preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 60nm, and ball internal cavity structure is less obvious, and topography uniformity is good.The mass percent that magnetic-particle accounts for shell is 50%.
Embodiment 4
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 10:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
4nano granule suspension, 3-(methacryloxypropyl) propyl trimethoxy silicane of 5mg and the isoamyl acetate of 0.01mL join in 5mL water, stir preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 60nm, and average shell thickness is about 20nm, and topography uniformity is good.The mass percent that magnetic-particle accounts for shell is 50%.
Embodiment 5
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 0.1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
4nano granule suspension, 3-(methacryloxypropyl) propyl trimethoxy silicane of 50mg and the isoamyl acetate of 1mL join in 5mL water, stir preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 100nm, and average shell thickness is about 20nm, and topography uniformity is poor.The mass percent that magnetic-particle accounts for shell is 9.1%.
Embodiment 6
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 0.1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
4nano granule suspension, 3-(methacryloxypropyl) propyl trimethoxy silicane of 50mg and the isoamyl acetate of 1mL join in 5mL water, stir preparation emulsion under 40 DEG C of environment.Emulsion is heated to 100 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The average particulate diameter of the product magnetic hollow nanosphere of gained is about 80nm, and average shell thickness is about 30nm, and topography uniformity is good.The mass percent that magnetic-particle accounts for shell is 9.1%.
Comparative example 1
Be the Fe of 6nm by average particulate diameter
3o
4nano particle adds containing in a certain amount of tetramethylammonium hydroxide aqueous solution, wherein Fe
3o
4the mass ratio of nano particle and Tetramethylammonium hydroxide is 0.1:1, and ultrasonic disperse makes particle surface adsorb Tetramethylammonium hydroxide, then Magnetic Isolation removes the Tetramethylammonium hydroxide not being adsorbed on particle surface, is mixed with the Fe that concentration is 5mg/mL
3o
4nano granule suspension.Then, 1mL Fe is got
3o
43-(methacryloxypropyl) propyl trimethoxy silicane of nano granule suspension and 50mg joins in 5mL water, does not add effumability solvent, stirs preparation emulsion under 30 DEG C of environment.Emulsion is heated to 70 DEG C, then adds initiator potassium persulfate 2mg after stirring 24h by emulsion.After stirring 24h, dry under 100 DEG C of environment, obtain product magnetic hollow nanosphere;
The product of gained is full particle, and average particulate diameter is about 60nm, and topography uniformity is poor.
Claims (10)
1. a magnetic hollow nanosphere, it is characterized in that, the shell of described magnetic hollow nanosphere is the silicon-containing polymer containing magnetic-particle, wherein, silicon-containing polymer comprises the product be polymerized by the methoxy silane containing double bond functional group or Ethoxysilane, magnetic-particle comprises ferriferous oxide and/or the ferriferous oxide of other metal that adulterates, and the particle diameter of described magnetic hollow nanosphere is 50 nm-1 μm, and shell thickness is 20nm-500nm.
2. magnetic hollow nanosphere according to claim 1, is characterized in that, the mass percent that magnetic-particle accounts for shell is 0.02%-90.9%, and the particle diameter of magnetic-particle is 1nm-20nm.
3. magnetic hollow nanosphere according to claim 1 and 2, is characterized in that, the particle diameter of magnetic hollow nanosphere is 50nm-150nm, shell thickness is 40nm-500nm, shell has nano-pore, and aperture is 0.1 nm-10nm, and the aperture of preferred nano-pore is 1nm-2nm.
4., according to described magnetic hollow nanosphere arbitrary in claim 1-3, it is characterized in that, magnetic-particle comprises at least one in tri-iron tetroxide, di-iron trioxide, four oxygen two cobalt ferrites, and the particle diameter of magnetic-particle is 3 nm-10nm.
5. the preparation method of arbitrary described magnetic hollow nanosphere in claim 1-4, is characterized in that, comprising:
1) magnetic-particle is added in the aqueous solution of dispersion stabilizer, first dispersed, be then separated the dispersion stabilizer removed and do not adsorb magnetic-particle, obtain the suspension being dispersed with magnetic-particle;
2) suspension step 1) prepared, silane coupler and volatile organic solvent, be added to the water, and stirs and form emulsion;
3) by step 2) after the heating of the emulsion prepared, add polymerization initiator wherein for initiated polymerization;
4) treat in step 3) after solution reaction, separation, drying obtain described magnetic hollow nanosphere.
6. preparation method according to claim 5, is characterized in that, in step 1), the mass ratio of magnetic-particle and dispersion stabilizer is (0.1-10): 1, and in suspension, the concentration of magnetic-particle is 0.1-50 mg/mL;
Dispersion stabilizer comprises at least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, tetramethyl ammonium chloride, etamon chloride, 4-propyl ammonium chloride, 4 bromide, tetraethylammonium bromide, 4-propyl bromide, TBAB.
7. preparation method according to claim 5, is characterized in that, in step 1), dispersedly comprise ultrasonic disperse, separation method comprises centrifugal or Magnetic Isolation.
8. according to described preparation method arbitrary in claim 5-7, it is characterized in that, step 2) in, silane coupler comprises methoxy silane containing double bond functional group and/or Ethoxysilane, and volatile solvent comprises at least one in isobutyl acetate, butyl acetate, isoamyl acetate, pentyl acetate, hexyl acetate;
Suspension: silane coupler: the usage ratio of easy volatile solvent is 1 mL:(5 mg-500 mg): (0.01 mL-6mL); In emulsion, the concentration of silane coupler is 1 mg/mL-1000 mg/mL.
9. according to described preparation method arbitrary in claim 5-7, it is characterized in that, in step 3), polymerization initiator: the consumption mol ratio of silane coupler is (0.1-10): 1, and polymerization initiator comprises persulfate, hydrogen peroxide and/or water-soluble azo initiator.
10., according to described preparation method arbitrary in claim 5-8, it is characterized in that, step 2) in, mixing time is greater than 0.5 hour, preferably 24 hours-48 hours;
In step 3), emulsion heating-up temperature is higher than 50 DEG C, and preferably 60 DEG C-70 DEG C, polymerization reaction time is greater than 0.1 hour, preferably 12 hours-24 hours;
In step 4), baking temperature higher than 30 DEG C, preferably 100 DEG C-150 DEG C.
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| CN107096039B (en) * | 2017-04-27 | 2019-11-26 | 武汉理工大学 | A kind of double medicines that carry of magnetic targeted pass release system and preparation method thereof |
| CN111672436A (en) * | 2020-05-21 | 2020-09-18 | 中国科学院化学研究所 | Flame-retardant phase-change microcapsule and preparation method and application thereof |
| CN112295542A (en) * | 2020-10-12 | 2021-02-02 | 四川大学 | Magnetic super-hydrophobic hollow carbon microsphere, preparation method and application |
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