CN107610874A - A kind of water-base magnetic liquid and preparation method thereof - Google Patents
A kind of water-base magnetic liquid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of water-base magnetic liquid and preparation method thereof, the preparation method comprises the following steps：1）, prepare Fe2+And Fe3+Molysite precursor solution, the excessive aqueous slkali dissolved with carboxymethyl chitosan is added into molysite precursor solution, under nitrogen protective condition, in certain temperature reaction for a period of time, that is, obtains magnetic liquid；2）, magnetic liquid purifying and individual layer cladding handle：By 1）Obtained magnetic liquid is centrifuged successively, and after removing precipitation, ultrafiltration is being carried out after solution is carried out into ultrasound.Characteristic of the preparation method of the water-base magnetic liquid of the present invention according to carboxymethyl chitosan, the ultrasound for increasing specified conditions in purge process carry out individual layer cladding processing, enhance the magnetic of water-base magnetic liquid.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of water-base magnetic liquid and preparation method thereof.
Background technology
Magnetic liquid is a kind of Nano-function thin films, is by grain size 10nm of surfactant cladding or so
Magnetic-particle be dispersed in base load liquid, formed a kind of nanoscale, solid-liquid two-phase stable homogeneous mixing soliquid,
Layering and precipitating does not occur under impressed field.Magnetic liquid is a kind of mobility for having liquid concurrently and solid magnetic material to magnetic field
A kind of new function material of response characteristic, therefore, it is widely used in the multiple fields such as chemical industry, biology and clinical medicine.
Magnetic-particle can be divided into according to classification：Metal class, there are Fe, Co, Ni, Fe-Co, Fe-Ni alloy/C etc.；Nitrided iron class,
There are FeN, Fe3N, Fe4N, Fe16N2（Or Fe8N) etc.；Metal oxide-type, mainly there are Fe3O4, γ-Fe2O3, MFe2O4 (M
=Co, Mn, Ni etc.）.Fe3O4 magnetic-particles can be magnetized rapidly under additional magnetic fields, after externally-applied magnetic field removes
Magnetic disappears immediately again, no coercivity and remanent magnetism, shows excellent superparamagnetism, thus has special physical and chemical performance
With nanometer performance.
Base load liquid mainly has water or the aqueous solution, hydrocarbon, organic silicone oil perfluorinated liquids etc. as magnetic-particle
Carrier fluid.Corresponding carrier fluid is selected according to magnetic liquid difference purposes, with the mostly oil base class such as damping on mechanical seal, loudspeaker
Magnetic liquid, and the magnetic liquid being applied to pharmaceutically is usually then using water as carrier fluid.Shell is used in patent CN 1702782A
Derivative-carboxymethyl chitosan of glycan is as synthesis of surfactant Fe3O4 magnetic-particle water-base magnetic liquids, the magnetic liquid
Body has biocompatibility, suitable for medical domain；Its preparation method used is adds surface while magnetic particle is synthesized
Activating agent makes synthesis and modified synchronous progress, and in charging, carboxymethyl chitosan is relative to Fe3O4It is excessive, due to synthesis with
Modification is carried out simultaneously, and its reaction sequence and the extent of reaction are uncontrollable, the Fe that will be there are3O4The surface of magnetic-particle outer cladding
Activating agent is multilayer, and generates later Fe3O4The situation that magnetic-particle can not be coated completely, and if carboxymethyl chitosan
Add excessively, will seriously cause Fe3O4Magnetic-particle multilayer coating structure.And the purge process in the patent be merely able to remove not by
The Fe coated completely3O4Magnetic-particle and uncoated carboxymethyl chitosan, the Fe of multilayer coating structure can not be removed3O4Magnetic-particle
The carboxymethyl chitosan of excess surface, become the Fe of individual layer cladding3O4Magnetic-particle, therefore influence whether final obtained
The magnetic of magnetic liquid, so as to influence to apply.
The content of the invention
Based on technical problem existing for background technology, the present invention propose a kind of water-base magnetic liquid preparation method and its
The water-base magnetic liquid of preparation.Characteristic of this method according to carboxymethyl chitosan, increase the processing of individual layer cladding in purge process,
Enhance the magnetic of water-base magnetic liquid.
Technical scheme is as follows：
A kind of preparation method of water-base magnetic liquid, comprises the following steps：
1）, prepare Fe2+And Fe3+Molysite precursor solution, added into molysite precursor solution and excessive be dissolved with carboxymethyl
The aqueous slkali of chitosan, under nitrogen protective condition, a period of time is reacted in certain temperature, that is, obtains magnetic liquid；
2）, magnetic liquid purifying and individual layer cladding handle：By 1）Obtained magnetic liquid is centrifuged successively, removes precipitation
Afterwards, ultrafiltration is being carried out after solution being carried out into ultrasound；It is centrifuged off failing the Fe being wrapped by completely3O4Magnetic-particle, because surface does not have
Have and coated by carboxymethyl chitosan, easily reunited, can settle down and remove after centrifugal treating；Ultrasound can make Fe3O4Magnetic
Particle surface, which adsorbs excessive carboxymethyl chitosan and come off, is changed into free carboxymethyl chitosan, and ultrafiltration removes free carboxymethyl chitosan
Sugar.Because carboxymethyl chitosan relies on carboxyl, amino, alcoholic extract hydroxyl group and Fe3O4Magnetic-particle surface action and adsorb in Fe3O4Magnetic
Property particle on formed individual layer cladding, and unnecessary carboxymethyl chitosan be with intermolecular hydrogen bond action adsorb in Fe3O4Magnetic
On the individual layer clad of grain, it under certain ultrasound condition, can depart from the carboxymethyl chitosan of unnecessary absorption, and monolayer adsorption
Carboxymethyl chitosan still stable absorption.
Preferably, the configuration of the molysite precursor solution is specially：It is 60%-70% that ferric trichloride is made into mass concentration
The aqueous solution, by ferrous chloride be configured to concentration be 15%-30% the aqueous solution, according to Fe2+：Fe3+ = 1:1.5-2 mol ratio
Two kinds of solution are mixed and are made into molysite mixed solution.
Preferably, the aqueous slkali is 25% ammoniacal liquor.
Preferably, by carboxymethyl chitosan and 25% ammoniacal liquor with mass ratio 1:5-30 wiring solution-formings, heating make carboxymethyl chitosan
Sugar is completely dissolved.It is highly preferred that the mass ratio of carboxymethyl chitosan and 25% ammoniacal liquor is 1:5-20.
Preferably, when the excessive aqueous slkali dissolved with carboxymethyl chitosan is added into molysite precursor solution, carboxylic first
The mol ratio of base enclosure glycan and Fe elements is 1-6:1；It is highly preferred that the mol ratio of carboxymethyl chitosan and Fe elements is 1:1 or
2:1。
Preferably, 1）Described in certain temperature be r.t.-100 DEG C, be for a period of time 0.5-2 h.
Preferably, the ultrasound condition is：Frequency is 20-50 kHz, and power is 120-300 W；It is highly preferred that frequency is
20-30 kHz, power are 120-200 W.
The present invention also provides the water-base magnetic liquid that above-mentioned preparation method obtains.
The present invention is advantageous in that：
Characteristic of the preparation method of the water-base magnetic liquid of the present invention according to carboxymethyl chitosan, increases specific in purge process
The ultrasound of condition carries out individual layer cladding processing, enhances the magnetic of water-base magnetic liquid.
Embodiment
Embodiment 1
By FeC13The aqueous solution that mass concentration is 60% is made into, by FeCl2The aqueous solution that concentration is 15% is configured to, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 1.5 mol ratio.By carboxymethyl chitosan and 25% ammoniacal liquor with
Mass ratio 1:5 wiring solution-formings, heating are completely dissolved carboxymethyl chitosan.The dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the mol ratio for making carboxymethyl chitosan and Fe elements is 1:1；Stir at ambient temperature
React 0.5 h.React and removing precipitation is centrifuged, the magnetic liquid that must stablize, then carried out ultrafiltration, frequency 20
KHz, power are 120 W, remove free state carboxymethyl chitosan present in magnetic liquid using ultrafiltration method, finally stablize magnetic
The saturation magnetization of property liquid is 0.45 em μ/g.
Embodiment 2
By FeC13The aqueous solution that mass concentration is 65% is made into, by FeCl2The aqueous solution that concentration is 20% is configured to, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 1.7 mol ratio.By carboxymethyl chitosan and 25% ammoniacal liquor with
Mass ratio 1:10 wiring solution-formings, heating are completely dissolved carboxymethyl chitosan.Added into molysite precursor solution excessive molten
When solution has the aqueous slkali of carboxymethyl chitosan, the mol ratio for making carboxymethyl chitosan and Fe elements is 3:1；Under the conditions of 50 DEG C
The h of stirring reaction 1.React and removing precipitation is centrifuged, the magnetic liquid that must stablize, then carried out ultrafiltration, frequency 25
KHz, power are 150 W, remove free state carboxymethyl chitosan present in magnetic liquid using ultrafiltration method, finally stablize magnetic
The saturation magnetization of property liquid is 0.51 em μ/g.
Embodiment 3
By FeC13The aqueous solution that mass concentration is 70% is made into, by FeCl2The aqueous solution that concentration is 30% is configured to, according to Fe2+：
Fe3+ = 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 mol ratio.By carboxymethyl chitosan and 25% ammoniacal liquor with matter
Measure ratio 1:20 wiring solution-formings, heating are completely dissolved carboxymethyl chitosan.The dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the mol ratio for making carboxymethyl chitosan and Fe elements is 6:1；Stirred under the conditions of 100 DEG C
Mix 2 h of reaction.React and removing precipitation is centrifuged, the magnetic liquid that must stablize, then carried out ultrafiltration, frequency 30
KHz, power are 200 W, remove free state carboxymethyl chitosan present in magnetic liquid using ultrafiltration method, finally stablize magnetic
The saturation magnetization of property liquid is 0.53 em μ/g.
Embodiment 4
By FeC13The aqueous solution that mass concentration is 65% is made into, by FeCl2The aqueous solution that concentration is 15% is configured to, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 mol ratio.By carboxymethyl chitosan and 25% ammoniacal liquor with matter
Measure ratio 1:30 wiring solution-formings, heating are completely dissolved carboxymethyl chitosan.The dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the mol ratio for making carboxymethyl chitosan and Fe elements is 2:1；Stir at ambient temperature
React 0.5 h.React and removing precipitation is centrifuged, the magnetic liquid that must stablize, then carried out ultrafiltration, frequency 50
KHz, power are 300 W, precipitate, illustrate that ultrasonic power is somewhat high, and the carboxymethyl chitosan for individual layer cladding occur comes off,
Reunite under ultrasound condition, so as to precipitate.Ultrafiltration method is used to remove free state carboxylic present in magnetic liquid after removing precipitation
Methyl chitosan, the saturation magnetization for finally stablizing magnetic liquid is 0.48 em μ/g.
Comparative example 1
By FeC13The aqueous solution that mass concentration is 65% is made into, by FeCl2The aqueous solution that concentration is 15% is configured to, according to Fe2+：
Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 2 mol ratio.By carbonyl methyl chitosan and 25% ammoniacal liquor with matter
Measure ratio 1:30 wiring solution-formings, heating are completely dissolved carbonyl methyl chitosan.The dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carbonyl methyl chitosan, the mol ratio for making carbonyl methyl chitosan and Fe elements is 2:1；Stir at ambient temperature
React 0.5 h.React and removing precipitation is centrifuged, the magnetic liquid that must stablize, further removed using ultrafiltration method
The free state carbonyl methyl chitosan do not adsorbed present in magnetic liquid by magnetic-particle, finally stablize the full of magnetic liquid
It is 0.32 em μ/g with the intensity of magnetization.
Embodiment 1-4 carries out individual layer cladding processing in purge process using ultrasound, and comparative example 1 is in purge process
Directly centrifuged and ultrafiltration, without the processing of individual layer cladding, can be seen that from saturation magnetization, processing gained is coated by individual layer
The saturation magnetization of water-base magnetic liquid be above not carrying out the water-base magnetic liquid of individual layer cladding processing.Also, super
Acoustic frequency reaches 50 kHz, when power is 300 W, the carbonyl methyl chitosan of individual layer cladding occurs because ultrasound intensity is too high
Come off so as to sedimentation of reuniting.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of water-base magnetic liquid, it is characterised in that comprise the following steps：
1）, prepare Fe2+And Fe3+Molysite precursor solution, added into molysite precursor solution and excessive be dissolved with carboxymethyl
The aqueous slkali of chitosan, under nitrogen protective condition, a period of time is reacted in certain temperature, that is, obtains magnetic liquid；
2）, magnetic liquid purifying and individual layer cladding handle：By 1）Obtained magnetic liquid is centrifuged successively, removes precipitation
Afterwards, ultrafiltration is being carried out after solution being carried out into ultrasound.
2. preparation method according to claim 1, it is characterised in that the configuration of the molysite precursor solution is specially：
Ferric trichloride is made into the aqueous solution that mass concentration is 60%-70%, it is the water-soluble of 15%-30% that ferrous chloride is configured into concentration
Liquid, according to Fe2+：Fe3+= 1:Two kinds of solution are mixed and are made into molysite mixed solution by 1.5-2 mol ratio.
3. preparation method according to claim 1, it is characterised in that the aqueous slkali is 25% ammoniacal liquor.
4. preparation method according to claim 3, it is characterised in that by carboxymethyl chitosan and 25% ammoniacal liquor with mass ratio
1:5-30 wiring solution-formings, heating are completely dissolved carboxymethyl chitosan.
5. preparation method according to claim 3, it is characterised in that the mass ratio of carboxymethyl chitosan and 25% ammoniacal liquor is
1:5-20。
6. preparation method according to claim 1, it is characterised in that the dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the mol ratio of carboxymethyl chitosan and Fe elements is 1-6:1.
7. preparation method according to claim 1, it is characterised in that the dissolving of excess is added into molysite precursor solution
When having the aqueous slkali of carboxymethyl chitosan, the mol ratio of carboxymethyl chitosan and Fe elements is 1:1 or 2:1.
8. preparation method according to claim 1, it is characterised in that 1）Described in certain temperature be r.t.-100 DEG C, one
The section time is 0.5-2 h.
9. preparation method according to claim 1, it is characterised in that the ultrasound condition is：Frequency is 20-50 kHz,
Power is 120-300 W；It is highly preferred that frequency is 20-30 kHz, power is 120-200 W.
A kind of 10. water-base magnetic liquid according to obtained by any described preparation methods of claim 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108389677A (en) * | 2018-04-27 | 2018-08-10 | 熊振 | A kind of preparation method of novel water-based magnetic liquid |
| CN108682530A (en) * | 2018-04-27 | 2018-10-19 | 熊振 | A kind of water-base magnetic liquid and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1059174A1 (en) * | 1999-06-10 | 2000-12-13 | Agfa-Gevaert N.V. | Acid stable aqueous dispersion of metal particles and applications |
| CN1468278A (en) * | 2000-10-05 | 2004-01-14 | �ն��о������ | Uv-assisted grafting of pes and psf membranes |
| CN1702782A (en) * | 2005-05-25 | 2005-11-30 | 中山大学 | Water-based magnetic liquid and method for making same |
| CN101792116A (en) * | 2009-05-25 | 2010-08-04 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
| CN107039139A (en) * | 2017-05-04 | 2017-08-11 | 绵阳市宏扬科技有限公司 | A kind of preparation method of magnetic fluid and its magnetic fluid of preparation |
-
2017
- 2017-10-18 CN CN201710969485.9A patent/CN107610874A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1059174A1 (en) * | 1999-06-10 | 2000-12-13 | Agfa-Gevaert N.V. | Acid stable aqueous dispersion of metal particles and applications |
| CN1468278A (en) * | 2000-10-05 | 2004-01-14 | �ն��о������ | Uv-assisted grafting of pes and psf membranes |
| CN1702782A (en) * | 2005-05-25 | 2005-11-30 | 中山大学 | Water-based magnetic liquid and method for making same |
| CN101792116A (en) * | 2009-05-25 | 2010-08-04 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
| CN107039139A (en) * | 2017-05-04 | 2017-08-11 | 绵阳市宏扬科技有限公司 | A kind of preparation method of magnetic fluid and its magnetic fluid of preparation |
Non-Patent Citations (2)
| Title |
|---|
| 夏平: "一种可见光响应纳米TiO2催化剂表面吸附特性及超声处理作用", 《稀有金属材料与工程》 * |
| 郑水林: "粉体表面改性", 《粉体表面改性》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108389677A (en) * | 2018-04-27 | 2018-08-10 | 熊振 | A kind of preparation method of novel water-based magnetic liquid |
| CN108682530A (en) * | 2018-04-27 | 2018-10-19 | 熊振 | A kind of water-base magnetic liquid and preparation method thereof |
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