CN1269769C - Method for preparing composite magneticparticle in submicro size by using Nano granules of magnet ironoxide to clad organic microsphere - Google Patents
Method for preparing composite magneticparticle in submicro size by using Nano granules of magnet ironoxide to clad organic microsphere Download PDFInfo
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- CN1269769C CN1269769C CN 03109800 CN03109800A CN1269769C CN 1269769 C CN1269769 C CN 1269769C CN 03109800 CN03109800 CN 03109800 CN 03109800 A CN03109800 A CN 03109800A CN 1269769 C CN1269769 C CN 1269769C
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Abstract
The present invention belongs to the technical field of rapidly coating organic submicron granules by using a ferrum collosol hydrolysis method, particularly to a method for coating organic microspheres by using nanometer magnetic ferric oxide granules to prepare composite submicron granules. Organic microspheres such as polystyrenes with different grain diameters, etc., can be obtained by using soap free emulsion. By using ferrous salt solution, the concentration of the ferrous salt solution in microsphere coating systems is controlled by using a slow injection method to obtain composite magnetic microspheres having different thickness of casing layers and core / casing structures. Thus, dimensions of magnetic cores and magnetic casings of the composite microspheres can be effectively controlled.
Description
Invention field
The invention belongs to the technical field that is covered with the machine submicron particles with ferrum collosol hydrolysis method Fast Packet, particularly coat the method that organic microballoon prepares compound submicron particles with the nano magnetic iron oxide particle.
Background technology
Recently, people are obtaining very big progress aspect the design of being devoted to have the specific function nano structural material and the research, the value of nano material is that it has character such as light, electricity, magnetic, mechanics, chemistry, and these character are because the ordered structure of the size of nano material, composition determines.Magnetic Nano material is because its distinctive magnetic property at first is used to biological field, as the biochemical drug and the magnetic guiding medicine of isolated genes; Also be used for the information storage material in a large number now.Therefore magnetic nanometer composite material is extensively used in fields such as Communication Engineering, pharmacy, biology.Generally be to be core with the sub-micron ball, nanocrystal is coated on outside the ball as shell, forms compound sub-micron ball with this.The nuclear that pattern, size, structure can arbitrarily be controlled over past ten years/hull shape magnetic Nano material has begun to be applied in fields such as telecommunications, catalysis, bioseparation, medical images diagnosis, magnetic cooling and magnetic fluid.
The technology of preparing that coats microballoon with nanoparticle is how relevant with particle surface physics and chemical property, there are many complicated factors to influence coating technology, as the change in electrical charge of outer shell, the chemical reaction ability of nuclear surface chemistry functional group, the dispersiveness of nuclear and stable.The physical properties of coating layer has also determined the dispersion stabilization of composite particles, and influences the magnetic of composite particles, photosensitiveness, catalytic.The problem that present people are concerned about most is how to improve the homogeneity of coating layer and the controllability of dispersion stabilization and coating.Recent years, scientific research group is arranged in the world also making up photonic crystal and three-dimensional porous material, in the hope of obtaining up-to-date optical communication material with this magnetic composite.In the past the research of complex microsphere was focused mostly on and be masterplate with the polystyrene, preparing them as shell material with silicon-dioxide and metallic oxide nanocrystal body.As clad nano silicon-dioxide, titanium dioxide, yttrium oxide or ferric oxide on polystyrene microsphere.Make polymer microballoon in many fields of hi-tech, obtain application like this.
People such as U.S. J.Ughelstad disclose 2.8 microns synthesis techniques to 4.5 microns magnetic polymer particles in US Patent PCT/NO83/00014, it is resulting to be the inside that magnetic-particle irregularly is distributed in polymer drops.Coating organic ball at preparation nano magnetic iron oxide particle recently prepares in the technology of compound sub-micro ball, upward (see also Frank Caruso with people such as Frank Caruso " chemical material " (calendar year 2001s 13 are rolled up 109 pages) and " science " (volume was 1111 pages in 1998 282) with layer-layer coating method, Marina Spasova, Andrei Susha.Chem.Mater..2001,13,109-116.and Caruso, F.; Caruso, R.A.; Mohwald, H.Science 1998,282, and 1111), and the even polymerization of magnetic grain of Benedikt Lindlar (sees also " material progress ", rolled up 1656 pages in 2002 14; Benedikt Lindlar, Monica Boldt, StefanieEiden-Assmann, Georg Maret, Adv.Mater.2002,14,1656.) be fresh approach.The former is the surface charge that changes polystyrene microsphere with polyelectrolyte, form by electrostatic attraction absorption nano magnetic iron oxide particle and coat shell, but repeated multiple times coats the control shell thickness like this.But in the method, the nano magnetic iron oxide granules preparation need be carried out in advance; And when control coats the thickness of shell, need many times carry out modification to the surface of microballoon, changing its surface charge property repeatedly, thereby make cladding process and step very loaded down with trivial details, can't use in practice with different polyelectrolyte.The latter adopts the even polymerization process of magnetic grain, need prepare nano magnetic particle in advance equally, and magnetic-particle is distributed evenly at composite particles inside; This loaded down with trivial details technology also can't obtain the outside evenly composite particles of coated magnetic housing.In a word, loaded down with trivial details preparation technology will make these ferric oxide coating technologies can't effectively be used in practice.
Summary of the invention
The object of the present invention is to provide with the nano magnetic iron oxide particle and coat the method that organic microballoon prepares compound submicron particles.The technology of this method is simple, and effective controlling packet coating layer ranges in thickness.
The objective of the invention is to be achieved through the following technical solutions:
The present invention is to use divalent iron salt solution control hydrolysis method to prepare magnetic iron oxide particle it is coated on organic microballoons such as polystyrene, thereby obtains the martial ethiops complex microsphere of core/shell structure.
The present invention controls the concentration of divalent iron salt solution in these microballoon coating systems by slow injecting method, can obtain the complex microsphere of different shell thicknesses, and the nucleocapsid size of complex microsphere can obtain effectively control like this.
The step of concrete grammar comprises:
Coat the preparation compound ball: take from system or the commercially available organic microballoon emulsion of copolymerization, adding is the deionized water dilution of 8～15 times of polystyrene microsphere emulsion volumes and stirs, add saltpetre, hexamethylenetetramine and deionized water then, stir and mix, under nitrogen or protection of inert gas, drip divalent iron salt solution with syringe pump, slowly be warming up to 70～120 ℃, 1～a few hours of successive reaction, obtain ferrum collosol; Centrifugation, washing and drying promptly obtains the compound submicron particles with organic microballoon of nano magnetic iron oxide particle coating.
The concentration of described polystyrene microsphere emulsion is 10～15wt%.
Divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.01～0.16: 0.003～0.01: 0.001～0.01: 50～170; Preferred divalent iron salt: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05～0.12: 0.005～0.01: 0.005～0.01: 55～160; Preferred divalent iron salt: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05～0.12: 0.005～0.009: 0.005～0.01: 60～150.
The particle diameter of described nano magnetic iron oxide crystal grain is 10～130 nanometers; The particle diameter of preferred nano crystal particles is 30～80 nanometers.
The particle diameter of the submicron particles of described polystyrene is 80～900 nanometers, is preferably 100～260 nanometers.
The rate of addition of described syringe pump is 0.01～1.0 ml/min, is preferably 0.1～0.5 ml/min.
Described divalent iron salt is iron protochloride or Iron diacetate etc.
Described rare gas element is argon gas or helium.
Raw material used in the present invention and technological process all do not have detrimentally affect to environment, and method of the present invention time-saving and efficiency is simple, are easy to apply, and can effectively control the thickness of compound submicron particles coating layer.
Purposes of the present invention: end-use of the present invention is extensive, be the basic raw material of high function magnetic fluid, magnetic refrigeration, information storage and bioseparation and catalytic material, can be applicable to fields such as catalystic material, high-performance stirring sealing, bio-pharmaceuticals and magnetic conductance electricity slurry.
Method of the present invention not only energy consumption is low, the product purity height, and good dispersity, and polymer microballoon surface magnetic particulate coated state can be controlled by changing reaction conditions.
Adopt method of the present invention to obtain the polymer microballoon/magnetic granules composite material of multiple coated state, as shown in Figures 1 and 2.
Description of drawings
Fig. 1. the polymer microballoon of embodiments of the invention 1/magnetic granules composite material electromicroscopic photograph.
Fig. 2. the polymer microballoon of embodiments of the invention 4/magnetic granules composite material electromicroscopic photograph.
Embodiment
Embodiment 1:
Get 60～80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30～100mmol saltpetre is added wherein, under agitation slowly be warming up to 80～100 ℃; 10～100mmol hexamethylenetetramine and 10～160mmol iron protochloride are respectively charged in the syringe, and the injection speed with 0.1～0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30～90 minutes.Centrifugation then, rotating speed are 1000～6000 rev/mins; After removing supernatant liquor, add 1.5 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 40～60 nanometers.
Embodiment 2:
Get 80～100 milliliters of the polystyrene microsphere emulsions of 340 nanometers, add 2.0 liters of distilled waters dilutions and stir.50～80mmol saltpetre is added wherein, under agitation slowly be warming up to 80～100 ℃; 10～100mmol hexamethylenetetramine and 50～120mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.1～0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30 minutes.Centrifugation then, rotating speed are 1000～4000 rev/mins; After removing supernatant liquor, add 2.0 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 340 nanometers, shell are the composite particles of 50～120 nanometers.
Embodiment 3:
Get 80～110 milliliters of the polystyrene microsphere emulsions of 320～380 nanometers, add 2800 milliliters of distilled waters dilutions and stir.50～80mmol saltpetre is added wherein, under agitation slowly be warming up to 80 ℃; 10～100mmol hexamethylenetetramine and 50～90mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.3～0.6 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30～90 minutes.Centrifugation then, rotating speed are 1000～2000 rev/mins; After removing supernatant liquor, add 3000 milliliters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 320～380 nanometers, shell are the composite particles of 30～60 nanometers.
Embodiment 4:
Get 80 milliliters of 300 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 3.0 liters of distilled waters and stir.50～80mmol saltpetre is added wherein, under agitation slowly be warming up to 70～95 ℃; 10～100mmol hexamethylenetetramine and 60～120mmol ferrous chloride are respectively charged in the syringe, and the injection speed with 0.1～0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection is respectively charged into 10～50mmol hexamethylenetetramine and 30～50mmol ferrous chloride in the syringe after finishing again, injects with the speed of 0.1～0.5 ml/min, has annotated the back and has continued reaction 30～40 minutes.Centrifugation then, rotating speed are 1000～3000 rev/mins; After removing supernatant liquor, add 3.0 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 300 nanometers, shell are the composite particles of 80～150 nanometer thickness.
Embodiment 5:
Get 30～40 milliliters of 160 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.20～60mmol saltpetre is added wherein; under agitation slowly be warming up to 80～100 ℃; 10～60mmol hexamethylenetetramine and 10～100mmol iron protochloride are respectively charged in the syringe; injection speed with 0.1～0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30～90 minutes.Centrifugation then, rotating speed are 1000～6000 rev/mins; After removing supernatant liquor, add 1.5 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 160 nanometers, shell are the composite particles of 20～50 nanometers.
Embodiment 6:
Get 60～80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30～100mmol saltpetre is added wherein, under agitation slowly be warming up to 80～100 ℃; 10～100mmol hexamethylenetetramine and 10～160mmol Iron diacetate are respectively charged in the syringe, and the injection speed with 0.1～0.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30～90 minutes.Centrifugation then, rotating speed are 1000～6000 rev/mins; After removing supernatant liquor, add 1.5 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 40～60 nanometers.
Embodiment 7:
Get 60～80 milliliters of 240 nano pipe/polyhenylethylene microballoon emulsions, add the dilution of 1.5 liters of distilled waters and stir.30～100mmol saltpetre is added wherein, under agitation slowly be warming up to 80～100 ℃; 10～100mmol hexamethylenetetramine and 10～180mmol Iron diacetate are respectively charged in the syringe, and the injection speed with 1.0～2.5 ml/min under feeding nitrogen protection slowly is added to it in system successive reaction.Injection finishes the back and continues reaction 30～90 minutes.Centrifugation then, rotating speed are 1000～6000 rev/mins; After removing supernatant liquor, add 1.5 liters of distilled water washings again, recentrifuge separates.Toasted 24 hours down at 70 ℃ at last, the particle diameter that promptly obtains examining is that 240 nanometers, shell are the composite particles of 20～60 nanometers.
Claims (8)
1. one kind coats the method that organic microballoon prepares compound submicron magnetic-particle with the nano magnetic iron oxide particle, it is characterized in that:
Get the polystyrene microsphere emulsion, adding is the deionized water dilution of 8～15 times of polystyrene microsphere emulsion volumes and stirs, add saltpetre, hexamethylenetetramine and deionized water then, stir, feeding dropping divalent iron salt solution under nitrogen or the protection of inert gas, slowly be warming up to 70～120 ℃, successive reaction obtains ferrum collosol; Centrifugation, washing and drying promptly obtains core/shell structure, the compound submicron particles of the organic microballoon that coats with the nano magnetic iron oxide crystal grain;
The concentration of described polystyrene microsphere emulsion is 10～15wt%;
Divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.01～0.16: 0.003～0.01: 0.001～0.01: 50～170.
2. the method for claim 1, it is characterized in that: the divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05～0.12: 0.005～0.01: 0.005～0.01: 55～160.
3. method as claimed in claim 2 is characterized in that: the divalent iron salt in the described ferrum collosol: saltpetre: hexamethylenetetramine: the mol ratio of water is 0.05～0.12: 0.005～0.009: 0.005～0.01: 60～150.
4. method as claimed in claim 3 is characterized in that: described rare gas element is argon gas or helium.
5. the method for claim 1, it is characterized in that: described nano magnetic iron oxide particle grain size is 30～80 nanometers.
6. the method for claim 1, it is characterized in that: described dropping divalent iron salt solution speed is 0.01～1.0 ml/min.
7. as claim 1,2,3 or 6 described methods, it is characterized in that: described divalent iron salt is iron protochloride or Iron diacetate.
8. the method for claim 1, it is characterized in that: described polystyrene microsphere particulate is of a size of 80～900 nanometers.
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| CN100408233C (en) * | 2006-08-23 | 2008-08-06 | 北京科技大学 | Magnetic field jel injection molding forming method for large scale rare earth aeolotropic binding magnet |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100408233C (en) * | 2006-08-23 | 2008-08-06 | 北京科技大学 | Magnetic field jel injection molding forming method for large scale rare earth aeolotropic binding magnet |
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