CN103657546A - Method for preparing nuclear shell type magnetic composite resin microballoons - Google Patents
Method for preparing nuclear shell type magnetic composite resin microballoons Download PDFInfo
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- CN103657546A CN103657546A CN201210353226.0A CN201210353226A CN103657546A CN 103657546 A CN103657546 A CN 103657546A CN 201210353226 A CN201210353226 A CN 201210353226A CN 103657546 A CN103657546 A CN 103657546A
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Abstract
The invention belongs to the technical field of function materials, and relates to a method for preparing nuclear shell type magnetic composite resin microballoons. The new method provided by the invention is a microwave hydrothermal method, the nucleus of the nuclear shell type magnetic composite microballoons is a magnetic ferroferric oxide nano cluster, and the shell layer is a phenolic resin. The preparation method comprises the steps of firstly preparing magnetic ferroferric oxide nanoparticles, taking the magnetic ferroferric oxide nanoparticles as seeds under the microwave hydrothermal condition, and covering phenol and methanal on the surface of ferroferric oxide through in situ polymerization. The preparation method provided by the invention has the advantages that the speed is high, the operation is simple, no surface active agent needs to be added, the process is controllable, the grain diameters of the obtained composite resin microballoons are uniform, the thickness of the shell layer is controllable, the magnetic responsibility is rapid, the stability is high, and the preparation method has good application prospect.
Description
Technical field
The invention belongs to technical field of function materials, relate to a kind of method of preparing core-shell type magnetic coupling resin microsphere, the magnetic coupling resin microsphere of preparing nucleocapsid structure that the method can be simple and quick.
Background technology
The magnetic composite microsphere of nucleocapsid structure is a kind of new function material, magnetic kernel and macromolecule shell, consists of.Described magnetic composite microsphere not only has the general character of numerous polymer microspheres, can at microsphere surface, introduce multiple reactive function base (as hydroxyl, sulfydryl, aldehyde radical, amino etc.) by chemical reactions such as copolymerization, surface modifications, also can by covalent bond, carry out the bioactivators such as desmoenzyme, cell, antibody, go back external magnetic field simultaneously and there is the functions such as targeting, magnetic thermotherapy and NMR imaging; Therefore, be widely used in field (Gao, the R.X. such as enrichment, separating-purifying, medicine and genophore, catalyst carrier and multi-modality imaging; He, X.W.; Chen, L.X.; Zhang, Y.K.J.Mater.Chem.2011,21,17863-1971).
At present, the preparation method of magnetic composite microsphere mainly contains emulsion polymerisation, precipitation polymerization, dispersin polymerization, mould plate technique and hydro-thermal method; Wherein, hydro-thermal method is a kind of easier method, as Gong(Fang, and Q.L.; Xuan, S.H.; Jiang.W.Q.; Gong, X.L.Adv.Funct.Mate.2011,21, the iron oxide (SPIO) of superparamagnetic of 1902-1909) etc. take is core, and silicic acid nickel (NS) is shell, and hydro-thermal reaction 36h under 190 ° of C has prepared magnetic composite microballoon.Jiang(Jiang, W.; Zhang, X.J.; Sun, Z.D.; Fang, Y.; Li, F.S.; Chen, K.; Huang C.G.Journal of Magnetism and Magnetic Materials 2011,323,2741-2747) seminar adopts hydro-thermal method to prepare Fe
3o
4@CP microballoon; Described shell raw material is polysaccharide, take NaOH as catalyst, under 180 ° of C, reacts after 15h, is coated on Fe
3o
4surface.This microballoon shell contains a large amount of hydroxyls and carboxyl, and average grain diameter is less than 300nm.(Feyen, the M. such as Lu; Weidenthaler, C.; Schuth, F.; Lu, A.H.J.Am.Chem.Soc., 2010,132,6791-6799) reported a kind of monodispersed Ag/Fe
3o
4compound microballoon, can be used for the electro-catalysis in organic synthesis; This kind of microballoon prepares at 160 ° of C hydro-thermal reaction 12h.
Although above-mentioned traditional hydro-thermal method is feasible, but the time that its obvious defect reaction consumes is long, generally need tens hours to tens hours, and the energy consuming in whole process is large, therefore, develop a kind of easy, fast again energy-conservation novel method to prepare core-shell type magnetic composite microsphere significant.
Summary of the invention
The object of the present invention is to provide a kind of easy, new method of preparing fast core-shell type magnetic coupling resin microsphere.The present invention is directed to existing problem in background technology, having proposed a kind of new method is microwave-hydrothermal method, has prepared fast, easily that to take ferroferric oxide magnetic nano bunch be core, the core-shell type magnetic resin microballoon that phenolic resins is shell.The present invention is achieved by the following technical solutions:
(1) first, take ferroferric oxide nano-clusters, formaldehyde, phenol is raw material, uniform and stable being dispersed in deionized water under ultrasonication;
(2) take ferroferric oxide magnetic nano bunch is seed, under the catalytic action of ammoniacal liquor, original position contracting between phenol and formaldehyde, the evenly poly-ferriferrous oxide nano-particle surface that is coated to, prepare and take ferriferrous oxide nano-particle as core, the core-shell type magnetic composite microsphere that phenolic resins is shell.
In preparation method of the present invention,
In described step (1), 5-200mg phenol is dispersed in 20mL deionized water, then add 0.15mL-0.5mL ammoniacal liquor (30%) and 10mg ferriferrous oxide nano-particle, after processing is uniformly dispersed, add formaldehyde 0.015mL-0.2mL, within ultrasonic 10 minutes, obtain the stable suspension that is uniformly dispersed;
In described step (2), the uniform and stable suspension obtaining in step (1) is transferred in microwave tube, under microwave, reacted.120 ℃-200 ℃ of microwave reaction temperature, reaction time 5min-40min minute, is cooled to room temperature by microwave tube and takes out.With magnetic separation, isolate product, and with deionized water and absolute ethanol washing reactant, with at 50 ℃ of vacuum drying ovens, within 4 hours, dry.
In the present invention, described method is microwave-hydrothermal method.
In the present invention, the described microwave reaction time only needs 20min.
In the present invention, described catalyst is ammoniacal liquor.
The magnetic composite microsphere core that the present invention makes is magnetic ferroferric oxide nanometer bunch, and shell is phenolic resins.
Preparation method's speed of the present invention is fast, simple to operate, do not need to add any surfactant, process is controlled; The magnetic composite microsphere compound with regular structure preparing, particle diameter distribution homogeneous, shell thickness is controlled, magnetic responsiveness is fast, stability is high, wherein, in described phenolic resins shell, there is the hydrophile function groups such as a large amount of phenolic hydroxyl groups, methylol, phenyl ring has hydrophobicity simultaneously, therefore have amphipathic, microballoon can stable dispersion at water, ethanol, acetone, nitrogen, in nitrogen-dimethyl formamide, acetonitrile equal solvent, be conducive to further functional modification, have good application prospect.
Accompanying drawing explanation
Fig. 1 prepares core-shell type magnetic resin microballoon flow chart in the present invention.
The perspective Electronic Speculum figure that Fig. 2 is the magnetic resin microballoon that uses new method of the present invention and prepare in the differential responses time, wherein,
（a）：5min，（b）10min，（c）20min，（d）40min。
Fig. 3 is the micro-magnetic saturation intensity figure of core-shell type magnetic resin.
Fig. 4 has shown dispersion stabilization and the magnetic responsiveness of magnetic composite microsphere of the present invention in water, ethanol, DMF and acetone.
The specific embodiment
Embodiment 1: tri-iron tetroxide magnetic bunch is 180nm left and right, and phenolic resins shell layer thickness is 10nm.
20mg phenol is dispersed in 20mL deionized water, then adds 0.15mL ammoniacal liquor and 10mg ferriferrous oxide nano-particle, after processing is uniformly dispersed, add formaldehyde 0.1mL, within ultrasonic 10 minutes, obtain the stable suspension that is uniformly dispersed.The uniform and stable suspension obtaining is transferred in microwave tube, under microwave, reacted.160 ℃ of microwave reaction temperature, react 5 minutes, microwave tube is cooled to room temperature and takes out.With magnetic separation, isolate product, and with deionized water and absolute ethanol washing reactant, with at 50 ℃ of vacuum drying ovens, within 4 hours, dry.
Embodiment 2: tri-iron tetroxide magnetic bunch is 180nm left and right, and phenolic resins shell layer thickness is 30nm.
Step is with described in embodiment 1, and different is that microwave heating time became 10min from 5min minute.
Embodiment 3: tri-iron tetroxide magnetic bunch is 180nm left and right, and phenolic resins shell layer thickness is 60nm.
Step is with described in embodiment 1, and different is that microwave heating time becomes 20min from 10min.
Embodiment 4: tri-iron tetroxide magnetic bunch is 180nm left and right, and phenolic resins shell layer thickness is 60nm.
Step is with described in embodiment 1, and different is that microwave heating time becomes 40min from 20min.
Claims (7)
1. a method of preparing the magnetic composite microsphere of nucleocapsid structure, is characterized in that, described compound resin microballoon core is that magnetic ferroferric oxide nanometer bunch, shell are phenolic resins; Described preparation method's step is:
(1) first, take ferroferric oxide magnetic nano bunch, formaldehyde, phenol is raw material, uniform and stable being dispersed in deionized water under ultrasonication;
(2) take ferroferric oxide magnetic nano bunch is seed, under the catalytic action of ammoniacal liquor, original position contracting between phenol and formaldehyde, the evenly poly-ferriferrous oxide nano-particle surface that is coated to, prepare and take ferriferrous oxide nano-particle as core, the core-shell type magnetic composite microsphere that phenolic resins is shell.
2. preparation method according to claim 1, it is characterized in that, in described step (1): 5-200mg phenol is dispersed in 20mL deionized water, then add 0.15mL ammoniacal liquor and 10mg ferriferrous oxide nano-particle, after processing is uniformly dispersed, add formaldehyde 0.015-0.2mL, within ultrasonic 10 minutes, obtain the stable suspension that is uniformly dispersed.
3. preparation method according to claim 1, is characterized in that, in described step (2): the uniform and stable suspension obtaining in step (1) is transferred in microwave tube, reacted under microwave.Microwave reaction temperature 120-200 ℃, reaction time 5-40 minute, is cooled to room temperature by microwave tube and takes out.With magnetic separation, isolate product, and with deionized water and absolute ethanol washing reactant, with at 50 ℃ of vacuum drying ovens, within 4 hours, dry.
4. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, described method is microwave-hydrothermal method.
5. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, described catalyst is ammoniacal liquor.
6. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, the described microwave reaction time is 20 minutes.
7. the described preparation method of one of claim 1-3 makes and take the magnetic composite microsphere that core is phenolic resins as magnetic ferroferric oxide nanometer bunch, shell.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126715A (en) * | 2015-08-29 | 2015-12-09 | 复旦大学 | Magnetic mesoporous silica microsphere material with yolk structure and preparing method thereof |
| CN106916586A (en) * | 2017-01-19 | 2017-07-04 | 安徽理工大学 | Phenolic resin is magnetic cup composite of matrix and its preparation method and application |
| CN108822581A (en) * | 2018-05-29 | 2018-11-16 | 上海应用技术大学 | A kind of hollow glass micropearl and preparation method thereof coating phenolic resin |
| CN109293860A (en) * | 2018-10-25 | 2019-02-01 | 齐鲁工业大学 | A kind of preparation method of magnetism yolk structure phenolic aldehyde resin microsphere |
| CN110115989A (en) * | 2019-06-11 | 2019-08-13 | 中国科学院长春应用化学研究所 | A kind of paramagnetism polymer composite microsphere and preparation method thereof |
| CN110183600A (en) * | 2019-05-31 | 2019-08-30 | 中国科学院长春应用化学研究所 | A kind of paramagnetism novolac polymer complex microsphere and preparation method thereof |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
Citations (1)
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| CN102151529A (en) * | 2011-02-11 | 2011-08-17 | 许昌学院 | Phenolic resin coated carbon nanotube composite material and chemical preparation method thereof |
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Patent Citations (1)
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| CN102151529A (en) * | 2011-02-11 | 2011-08-17 | 许昌学院 | Phenolic resin coated carbon nanotube composite material and chemical preparation method thereof |
Non-Patent Citations (1)
| Title |
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| LI-JUN YOU ET AL.: "Ultrafast Hydrothermal Synthesis of High Quality Magnetic Core Phenol–Formaldehyde Shell Composite Microspheres Using the Microwave Method", 《LANGMUIR》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126715A (en) * | 2015-08-29 | 2015-12-09 | 复旦大学 | Magnetic mesoporous silica microsphere material with yolk structure and preparing method thereof |
| CN106916586A (en) * | 2017-01-19 | 2017-07-04 | 安徽理工大学 | Phenolic resin is magnetic cup composite of matrix and its preparation method and application |
| CN108822581A (en) * | 2018-05-29 | 2018-11-16 | 上海应用技术大学 | A kind of hollow glass micropearl and preparation method thereof coating phenolic resin |
| CN108822581B (en) * | 2018-05-29 | 2020-07-28 | 上海应用技术大学 | Phenolic resin coated hollow glass bead and preparation method thereof |
| CN109293860A (en) * | 2018-10-25 | 2019-02-01 | 齐鲁工业大学 | A kind of preparation method of magnetism yolk structure phenolic aldehyde resin microsphere |
| CN109293860B (en) * | 2018-10-25 | 2021-03-26 | 齐鲁工业大学 | Preparation method of magnetic phenolic resin microspheres with yolk structures |
| CN110183600A (en) * | 2019-05-31 | 2019-08-30 | 中国科学院长春应用化学研究所 | A kind of paramagnetism novolac polymer complex microsphere and preparation method thereof |
| CN110115989A (en) * | 2019-06-11 | 2019-08-13 | 中国科学院长春应用化学研究所 | A kind of paramagnetism polymer composite microsphere and preparation method thereof |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
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Application publication date: 20140326 |