CN105854747B - A kind of monodisperse melamine resin magnetic microsphere and preparation method thereof - Google Patents
A kind of monodisperse melamine resin magnetic microsphere and preparation method thereof Download PDFInfo
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- CN105854747B CN105854747B CN201610275861.XA CN201610275861A CN105854747B CN 105854747 B CN105854747 B CN 105854747B CN 201610275861 A CN201610275861 A CN 201610275861A CN 105854747 B CN105854747 B CN 105854747B
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- magnetic microsphere
- melamine resin
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Abstract
The invention discloses a kind of monodisperse melamine resin magnetic microsphere and preparation method thereof, this method is using monodisperse melamine resin microballoon as template, the Fe for being 2 μm in microsphere surface package average grain diameter3O4Spherical shell solves Fe3O4The larger problem of density, magnetic microsphere partial size obtained is uniform, good dispersion, thermal stability is high and its microwave absorbing property is preferable, can be applied to the fields such as spacecraft, the energy, biological medicine.
Description
Technical field
The invention belongs to magnetic material technical field more particularly to a kind of monodisperse melamine resin magnetic microsphere and its
Preparation method.
Background technique
Monodisperse melamine resin (MF) microballoon is high (about 200 DEG C) using temperature, while its surface contains amino, hydroxyl etc. and lives
Property group, is easy to functionalization, there is good application potential；From principle, it is polycondensation that MF, which polymerize principle, and polymerization is generally adopted
With dispersion copolymerization method, this method has the characteristics that period short (about 40 minutes), simple process, microballoon monodispersity are good.
Magnetic responsiveness, magnetic effect and the macromolecule that monodisperse melamine resin magnetic microsphere has both magnetic inorganic substance simultaneously are micro-
Many surface-functionals of function base characteristic, skin effect and the bulk effect of ball etc., while ferrite absorbs energy because it has
The advantages that power is strong, cheap is the most common microwave absorbing material.
In ferrite, Fe3O4It is the hot spot of research and application, in various fields such as magnetic fluid, magnetic recording, biomedicines
Possess wide application.But Fe3O4Since density is larger, in the weight and the higher spacecraft neck of thickness requirement to microwave absorbing coating
Limited in domain, it is necessary to by Fe3O4Lighting.
CN101004414A discloses a kind of magnetic macromolecular microsphere and its synthesizing preparation method in situ, made from the invention
Microsphere diameter is 4 ~ 20 μm, and magnetic particle accounts for the 20 ~ 40% of polymer microsphere total weight.
CN1302831A discloses a kind of magnetic macromolecular microsphere and preparation method thereof, the invention propose it is a kind of have it is super suitable
The magnetic macromolecular microsphere that magnetic, magnetic particle is wrapped up by polymeric dispersant, microsphere diameter is between 0.1 ~ 10 μm, magnetic particles
Son accounts for about the 50 ~ 70% of polymer microsphere total weight.
CN10480127A discloses a kind of preparation method of magnetic microsphere, and this method uses iron ion and ferrous ion, system
Standby magnetic fluid, adds methyl methacrylate etc. and prepares microballoon, microballoon obtained can be used for during gene sequencing
The fixation of enzyme.
CN102921360A discloses a kind of Monodisperse magnetic microsphere and preparation method thereof, and this method is with melamino-formaldehyde
Resin (MF) microballoon is mother bulb, the catalytic action using noble metal to liquid phase chemical deposition, in MF microsphere surface deposited magnetic gold
Belong to, magnetic microsphere obtained has good application prospect in fields such as biomedicine, electromagnetism stealths.
CN104538145A discloses a kind of multiple dimensioned, uniform, Monodisperse magnetic microsphere and preparation method thereof, and this method is adopted
With mixed solvent thermal method, by adjust the volume fraction or iron and other transition metal salts of water the controllable particle of ratio and
Composition, magnetic microsphere obtained have broad application prospects in fields such as magnetorheological, medical diagnosis.
In conclusion the Monodisperse magnetic microsphere particle diameter distribution of existing method preparation is wide, the weak, complex process of magnetism, limit
The practical application of magnetic microsphere is made.
Summary of the invention
It is an object of the invention to for magnetic microsphere partial size existing in the prior art distribution is wide, magnetism is weak, technique is multiple
Miscellaneous problem provides a kind of preparation method of monodisperse melamine resin magnetic microsphere.This method utilizes highly homogeneous single point of partial size
Dissipating melamine resin microballoon is mother bulb, wraps up Fe in microsphere surface3O4Prepare magnetic microsphere.Preparation process of the present invention is easy, and gained is micro-
Ball density is smaller, good dispersion, thermal stability is high and its microwave absorbing property is good, can be applied to spacecraft, magnetic fluid, biology doctor
The fields such as medicine.
The preparation method of the monodisperse melamine resin magnetic microsphere, comprising the following steps:
Step 1: Fe2+The absorption of ion
MF microballoon after taking centrifugation to wash, dry weight about 1.4g continue 50-70 after ultrasonic disperse 5min in 50-70ml water
DEG C heating stirring；By Dissolvable Fe2+Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 0.2 ~ 1.2mol/L,
After 50-70 DEG C of heating stirring reaction 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 50-70ml water, ammonium hydroxide adjusts pH to 8.0-11.0；By gained mixed liquor
Static heating 4-7h at a temperature of 30 ~ 90 DEG C is washed after Magneto separate, after repeating 3-5 time both required magnetic microsphere sample.
Preferably, the preparation method of the monodisperse melamine resin magnetic microsphere, comprising the following steps:
Step 1: Fe2+The absorption of ion
MF microballoon after taking centrifugation to wash, dry weight about 1.4g continue 60 DEG C of heating in 60ml water after 5 min of ultrasonic disperse
Stirring；By Dissolvable Fe2+Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 1.2mol/L, and 60 DEG C of heating are stirred
After mixing reaction 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 60ml water, ammonium hydroxide adjusts pH to 10.0；By gained mixed liquor in 40-70
Static heating 4h at DEG C is washed after Magneto separate, after being repeated 3 times both needed for magnetic microsphere sample.
The Dissolvable Fe2+Solution is FeSO4、FeCl2Or mixtures thereof.
The pattern and performance characterization for the monodisperse melamine resin magnetic microsphere being prepared through the above steps are as follows:
For the magnetic microsphere using MF as core, 2 μm of Fe is wrapped up on surface3O4Spherical shell, partial size are 2-10 μm, and monodispersity is good
It is good.As MF micro-spheres Fe3O4Afterwards, microsphere surface roughness increases, and the concentration of ferrous ion, improves microballoon when increasing absorption
The Fe on surface3O4Covering amount.When adsorption concentration reaches 1.2 mol/L, the mass ratio of ferriferous oxide is close to 35%.There are resin balls
In the case where, the ferriferous oxide shell synthesized in thermal and hydric environment is 60 DEG C or so in Aging Temperature and reaches highest.Adsorption microspheres ratio
Saturation magnetization changes obviously with Aging Temperature, and specific saturation magnetization reaches maximum value 16.9Am at 60 DEG C2/kg。
The present invention forms Fe using monodisperse MF microballoon as template, in microsphere surface3O4The magnetic microsphere of clad, formation is close
Degree is smaller, solves Fe3O4The big problem of density.The preparation method of the magnetic microsphere is simple, easy to operate, required time
It is short, it is at low cost, it pollutes small.Resulting magnetic microsphere partial size is uniform controllably, heat resistance is good, microwave absorption property is good, solves
Before the distribution of magnetic microsphere partial size it is wide, magnetic weak the problems such as, there is good development prospect.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of magnetic microsphere prepared by embodiment 1；
Fig. 2 is the hysteresis loop of magnetic microsphere prepared by embodiment 4.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
Step 1: Fe2+The absorption of ion
MF microballoon (dry weight about 1.4g) after taking centrifugation to wash continues 60 DEG C after 5 min of ultrasonic disperse in 60 ml water and adds
Thermal agitation is uniform；By FeSO4Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 0.4mol/L, and 60 DEG C of heating are stirred
After mixing reaction 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 60ml water, ammonium hydroxide adjusts pH to 8.0, and mixed liquor is static at 40 DEG C
Heat 4h, washing sample after Magneto separate, magnetic microsphere sample needed for both obtaining after being repeated 3 times.
Embodiment 2
Step 1: Fe2+The absorption of ion
MF microballoon (dry weight about 1.4g) after taking centrifugation to wash continues 50 DEG C after ultrasonic disperse 5min in 50 ml water and adds
Thermal agitation is uniform；By FeCl2Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 1.2 mol/L, 60 DEG C of heating
After being stirred to react 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 50ml water, ammonium hydroxide adjusts pH to 10.0, and mixed liquor is quiet at 70 DEG C
Only heat 5h, washing sample after Magneto separate, magnetic microsphere sample needed for both obtaining after being repeated 5 times.
Embodiment 3
Step 1: Fe2+The absorption of ion
MF microballoon (dry weight about 1.4g) after taking centrifugation to wash continues 70 DEG C after ultrasonic disperse 5min in 70 ml water and adds
Thermal agitation is uniform；By FeSO4Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 0.2 mol/L, 70 DEG C of heating
After being stirred to react 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 60ml water, ammonium hydroxide adjusts pH to 11.0, and mixed liquor is quiet at 30 DEG C
Only heat 6h, washing sample after Magneto separate, magnetic microsphere sample needed for both obtaining after being repeated 3 times.
Embodiment 4
Step 1: Fe2+The absorption of ion
MF microballoon (dry weight about 1.4g) after taking centrifugation to wash continues 60 DEG C of heating in 60ml water after ultrasonic disperse 5min
It stirs evenly；By FeSO4 、FeCl2Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 1.0mol/L, 50 DEG C
After heating stirring reacts 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption.
Step 2: Fe2+The conversion and Chen Hua process of ion
MF microballoon obtained by step 1 is dispersed in 70ml water, ammonium hydroxide adjusts pH to 10.0, and mixed liquor is quiet at 90 DEG C
Only heat 7h, washing sample after Magneto separate, magnetic microsphere sample needed for both obtaining after being repeated 4 times.
Claims (5)
1. a kind of preparation method of monodisperse melamine resin magnetic microsphere, which comprises the following steps:
Step 1: Fe2+The absorption of ion
MF microballoon after taking centrifugation to wash, dry weight 1.4g continue 50-70 DEG C of heating in 50-70ml water after ultrasonic disperse 5min
Stirring；By Dissolvable Fe2+Solution is slowly added thereto, so that Fe in solution2+Ion concentration is 0.2 ~ 1.2 mol/L, 50-70
After DEG C heating stirring reaction 1h, it is centrifugated to obtain Fe2+The MF microballoon of ionic adsorption；
Step 2: Fe2+The conversion of ion and ageing process
MF microballoon obtained by step 1 is dispersed in 50-70ml water, ammonium hydroxide adjusts pH to 8-11；By gained mixed liquor 30 ~ 90
Static heating 4-7h at a temperature of DEG C is washed after Magneto separate, after repeating 3-5 time both required magnetic microsphere sample.
2. the preparation method of monodisperse melamine resin magnetic microsphere according to claim 1, which is characterized in that the step
Two: MF microballoon obtained by step 1 being dispersed in 60ml water, ammonium hydroxide adjusts pH to 10.0；By gained mixed liquor at 40-70 DEG C
Static heating 4h is washed after Magneto separate, after being repeated 3 times both needed for magnetic microsphere sample.
3. the preparation method of monodisperse melamine resin magnetic microsphere according to claim 1, which is characterized in that described solvable
Property Fe2+Solution is FeSO4、FeCl2Or mixtures thereof.
4. a kind of preparation method of monodisperse melamine resin magnetic microsphere according to claim 1-3 is prepared
Magnetic microsphere, which is characterized in that for the magnetic microsphere using MF as core, 2 μm of Fe is wrapped up on surface3O4Spherical shell, partial size 2-10
μm。
5. monodisperse melamine resin magnetic microsphere according to claim 4, which is characterized in that the magnetic microsphere is at 60 DEG C
When specific saturation magnetization reach 16.9Am2/kg。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772622A (en) * | 2005-10-08 | 2006-05-17 | 北京化工大学 | Surfactant intercalated magnetic hydrotalcite material and its prepn |
| CN102120168A (en) * | 2010-12-07 | 2011-07-13 | 复旦大学 | Multifunctional core-shell structure fluorescent coding magnetic microspheres and preparation method thereof |
| CN104907019A (en) * | 2015-04-29 | 2015-09-16 | 复旦大学 | Magnetic fluorescent Raman double-encoding composite microspheres and preparation method and application thereof |
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| US6793723B2 (en) * | 2001-05-10 | 2004-09-21 | Pitney Bowes Inc. | Homogeneous photosensitive optically variable ink compositions for ink jet printing |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772622A (en) * | 2005-10-08 | 2006-05-17 | 北京化工大学 | Surfactant intercalated magnetic hydrotalcite material and its prepn |
| CN102120168A (en) * | 2010-12-07 | 2011-07-13 | 复旦大学 | Multifunctional core-shell structure fluorescent coding magnetic microspheres and preparation method thereof |
| CN104907019A (en) * | 2015-04-29 | 2015-09-16 | 复旦大学 | Magnetic fluorescent Raman double-encoding composite microspheres and preparation method and application thereof |
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