CN101710514A - Magnetic nano-substance and preparation method thereof - Google Patents
Magnetic nano-substance and preparation method thereof Download PDFInfo
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- CN101710514A CN101710514A CN200910201399A CN200910201399A CN101710514A CN 101710514 A CN101710514 A CN 101710514A CN 200910201399 A CN200910201399 A CN 200910201399A CN 200910201399 A CN200910201399 A CN 200910201399A CN 101710514 A CN101710514 A CN 101710514A
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Abstract
The invention relates to a magnetic nano-substance and a preparation method thereof, an organic ligand of long-chain amine is coated on the surface of the magnetic nano-substance, the long-chain amine is taken as a surfactant, and a high-boiling point organic matter is taken as a solvent, thereby carrying out high-temperature degradation reaction on carbon-containing iron salt for preparing the magnetic nano-substance. The magnetic substance has the advantages of high stability, difficult oxidation and no toxicity or side effects, and can be encapsulated by a variety of capsules and be further used in biological bodies (such as biological medical materials); based on the good magnetic property, the magnetic substance can achieve the target by orientation under the action of an external magnetic field, thereby having the function of directional delivery and being excreted under the action of metabolism. The magnetic nano-substance can also applied in the fields like magnetic fluid, magnetic resonance imaging, sensors, data storage and the like.
Description
Technical field
The invention belongs to magnetic material and field of nanometer material technology, be specifically related to a kind of homodisperse nano-magnetic material and preparation method thereof in the middle of organic solvent that has.
Background technology
In present magnetisable material field, the preparation method adopts coprecipitation more, but the magnetisable material crystallinity of this method preparation is poor, and particle size distribution is uneven and mainly concentrate on big particle size range.And the big magnetic particle of particle diameter has dipole moment, makes the application of magnetic nano-particle be subjected to severely restricts.Magnetic particle wants to have superparamagnetism, and its particle diameter must be enough little, reaches the 10nm rank.If it is very attractive that the superparamagnetism of small particle diameter is applied to biological field, because by means of this character, magnetisable material is difficult to be gathered in vivo piece, and they are stable in the air simultaneously, can discharge naturally by metabolism in vivo.In order to obtain to have the magnetic thing of this character, be badly in need of a kind of better preparation means, the heat drop solution has also just been arisen at the historic moment.
It at first is to be applied on the cadmium selenide that the heat drop solution is used to prepare organo-metallic compound, along with the development of technology, is used to prepare magnetic metal particle and metal oxide particle gradually.This method is with respect to conventional method, has good size Control, narrower distribution of sizes and extraordinary crystallinity.Aspect size, traditional coprecipitation normal distribution standard deviation is between 0.2-0.4, and the heat drop solution has only about 0.1-0.15.Because the simple and good reproducibility of this method preparation, particle size homogeneous, crystallinity height, therefore adopted widely.
Thereby the heat drop solution mainly is to rely on heat that organo-metallic compound is decomposed to make magnetic particle.In course of reaction, normally at high temperature use high boiling organic solvent as part, mainly comprise the surfactant of some long-chains, such as materials such as oleic acid, alkylamines.These organic substances are adsorbed on particle surface, not only can strengthen the stability of product, and reaction is also had facilitation.The compounds such as iron pentacarbonyl, ferric acetyl acetonade and iron oleate that prepare by molysite can be used as the presoma of thermal degradation reaction, i.e. reactant.Features such as the size of magnetisable material, shape and particle size distribution are the difference to some extent along with the different of presoma all.The crystal particles that preparation has monodispersity mainly is divided into two steps, i.e. nucleation stage and growth phase.Nucleation stage is meant that in reaction solution the concentration of metal ion constantly raises along with the carrying out of degraded, and when concentration increased to above its supersaturation concentration, the one-tenth nuclear reaction of homogeneous will begin to carry out.The solute of plane of crystal of the arriving soon after crystal face of growing into increases crystal.
Summary of the invention
The object of the present invention is to provide a kind of magnetic nano-substance and preparation method thereof, prepare the little and uniform magnetisable material Fe of a kind of particle diameter by the thermal degradation method
3O
4, having excellent superparamagnetism, can also be dispersed in the organic solvent simultaneously.
For reaching above purpose, solution of the present invention is:
A kind of magnetic nano-substance, it is the nano-magnetic material that a kind of surface is coated by the organic ligand long-chain amine, the particle diameter of this material is very little, less than 10nm, can evenly disperse in organic solvent such as toluene, n-hexane, has extraordinary oil-soluble.Because of the outside coats organic ligand, be easy to preserve, stable performance is difficult for oxidized.
Described long-chain amine is octadecylamine, lauryl amine; Described nano-magnetic material is Fe
3O
4
A kind of preparation method of magnetic nano-substance is that surfactant, high boiling organic substance are solvent with the long-chain amine, the molysite of carbon containing is carried out the high temperature degradation reaction obtain this magnetic nano-substance Fe
3O
4, Fe
3O
4With surfactant, lauryl amine for example, thus generate the Fe that has organic ligand by the combination of duplet
3O
4The magnetic thing.The particle diameter of the nano-magnetic material that generates is lower than 20mm.
Further, it may further comprise the steps:
1) carbon containing molysite and long-chain amine were with 1: 2 mixed in molar ratio, and solvent dissolves carbon containing molysite and long-chain amine fully;
2) material heating and the feeding nitrogen to mixed dissolution in the step 1) stirs;
3) keep temperature stabilization, product is heated to and is black;
4) product with heat acetone solution and place centrifuge centrifugal, obtain end product nano-magnetic material.
Described carbon containing molysite is that ferric stearate, stearic acid are ferrous, iron oleate, iron pentacarbonyl; Described long-chain amine is octadecylamine, lauryl amine; Described solvent is a vaccenic acid.
Described step 2) in the mixed dissolution material is added the thermal recovery sand-bath.
Described temperature remains on 330-350 ℃.
Described acetone solvent temperature is controlled at 45-50 ℃.
Aforementioned magnetic nano-substance is coated by capsule, is used for medicine and carries.
Aforementioned magnetic nano-substance is applied to magnetic fluid, magnetic resonance imaging, transducer and storage.
The present invention adopts the ferrous degraded at high temperature of stearic acid to make product first, can obtain the nano particle of different-grain diameter by the consumption of reconciliation statement surface-active agent lauryl amine and solvent vaccenic acid, realizes the purpose of control reaction result.
Magnetisable material of the present invention is synthetic with following method: stearic acid is ferrous to be added according to 1: 2 mol ratio with the surfactant lauryl amine, mix in three-necked bottle with a certain amount of high-temperature solvent vaccenic acid subsequently, the consumption of vaccenic acid gets final product with solubilizing reaction thing fully.Imbed in the sand-bath and heat, feed nitrogen and constantly stir simultaneously, when temperature is raised to 330 ℃, keep temperature stabilization, continue heating 30 minutes, when product becomes black, take out, use the acetone solution of heat subsequently, because the boiling point of acetone is 55 ℃, so the temperature of hot acetone is controlled at about 45-50 ℃.Product places centrifuge centrifugal after with acetone solution again, removing vaccenic acid and free lauryl amine, thereby with the dry end-product that obtains of product.
Owing to adopted such scheme, the present invention to have following characteristics: synthesis step of the present invention is simple, separates and purifies conveniently, is easy to realize industrialization.This magnetisable material stability is higher, be difficult for oxidation, have no side effect, can be coated by multiple capsule and be used for (as bio-medical material) in the organism, based on its magnetic preferably, therefore can under the effect of externally-applied magnetic field, orientation arrive target position, have the function of directed transportation, and can under metabolic effect, can excrete.Also can be applied to such as fields such as magnetic fluid, magnetic resonance imaging, transducer and storage.
Description of drawings
Fig. 1 prepares the concrete reacting flow chart of nano-magnetic material for the present invention.
Fig. 2 is the Fe with organic ligand
3O
4Structure chart.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
Embodiment 1
2.5 the gram stearic acid is ferrous, 1.5 gram lauryl amines, promptly stearic acid ferrous with mol ratio lauryl amine be 1: 2, repeatedly experiment finds that the effect of this proportioning is best.The mixing of 10ml vaccenic acid is placed in the three-necked bottle, in heating, constantly also stir to wherein feeding nitrogen, when temperature is raised to 330 ℃, keep temperature constant, continue heating 30min, when the product color is black by red stain, take out, acetone with heat dissolves product subsequently, place centrifuge centrifugal (10000r/min), remove impurity, impurity mainly is unreacted raw material and free lauryl amine.The product that obtains at last is an ater, and magnetic is strong, can be dispersed in the organic solvent toluene, and its particle diameter is about 10nm.
Dried product is used magnetometer survey, and its magnetization can reach 30emu/g.
With embodiment 1, but the consumption of solvent vaccenic acid doubles, and reaches 20ml.The product for preparing under the equivalent responses condition can be seen the more even and crystal clear-cut of its particle diameter under transmission electron microscope, the magnetization reaches 40emu/g.This is because under situation about existing than multi-solvent, although its crystalline rate reduces, because ferrous disperse in solvent more even of stearic acid, has more fully the space carry out the crystallization of single particle, and all crystal forms is more complete, and magnetic property is also just higher.Its particle diameter and embodiment 1 do not have obviously difference, and just profile is more clear, and crystallization effect is better, thereby magnetic is also stronger.
Embodiment 3
With embodiment 1, the consumption of surfactant lauryl amine doubles, and is 3.0 grams, and the product of equal conditions preparation finds that through detecting crystalline form is not sufficiently complete, but the very little magnetization of particle diameter is also lower.The product that can see black after the product drying very easily becomes pitchy, and oxidation reaction has taken place in this explanation, Fe
3O
4Change Fe into
2O
3, separate out more white lauryl amine simultaneously.This is because under the excessive situation of surfactant, magnetisable material as yet crystallization fully its surface just absorption do not gone up the lauryl amine part, thereby stoped ion in the absorption of magnetic thing plane of crystal, cause the product crystallinity poor.The product particle diameter of this prepared in reaction is that profile is fuzzyyer about 8nm, and crystallinity is compared relatively poor with example 1 with example 2.
The particle diameter of magnetisable material of the present invention can be regulated and control by conditions such as control consumption of reactant and reaction time, experiment is found under the constant situation of other condition, the particle diameter that the consumption of lauryl amine increases product is littler, when prolonging the time of reaction, the particle diameter of product has increase slightly, but is no more than 10nm.
Generally speaking, the magnetic nano-substance particle diameter that the present invention makes is little and magnetic is stronger, and extraordinary superparamagnetism is arranged, and, therefore can disperse in the middle of organic solvent with the long-chain amine part based on its appearance.And this magnetisable material can be coated by multiple capsule be used for (as bio-medical material) in the organism, based on its magnetic preferably, therefore can be under the effect of externally-applied magnetic field the directed target position that arrives, have the function of directed transportation.
The present invention notes following 2 problems when being applied on the industry: the one, and the feeding speed of temperature and N2 must be controlled well in the course of reaction, because reaction temperature is about 350 ℃, this temperature has surpassed the boiling point of solvent vaccenic acid, therefore to note feeding the speed of N2, avoid too fast the vaporing away of solvent, cause producing failure.The 2nd, the attentive response thing to stir and to be heated evenly, thereby otherwise easily react and not exclusively cause product impure.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (10)
1. magnetic nano-substance, it is characterized in that: it is the nano-magnetic material that a kind of surface is coated by the organic ligand long-chain amine.
2. magnetic nano-substance as claimed in claim 1 is characterized in that: described long-chain amine is octadecylamine, lauryl amine; Described nano-magnetic material is Fe
3O
4
3. the preparation method of magnetic nano-substance as claimed in claim 1 is characterized in that: be that surfactant, high boiling organic substance are solvent with the long-chain amine, the molysite of carbon containing carried out the high temperature degradation reaction obtain this magnetic nano-substance.
4. the preparation method of magnetic nano-substance as claimed in claim 3, it is characterized in that: it may further comprise the steps:
1) carbon containing molysite and long-chain amine were with 1: 2 mixed in molar ratio, and solvent dissolves carbon containing molysite and long-chain amine fully;
2) material heating and the feeding nitrogen to mixed dissolution in the step 1) stirs;
3) keep temperature stabilization, product is heated to and is black;
4) product with heat acetone solution and place centrifuge centrifugal, obtain end product nano-magnetic material.
5. as the preparation method of claim 3 or 4 described magnetic nano-substances, it is characterized in that: described carbon containing molysite is that ferric stearate, stearic acid are ferrous, iron oleate, iron pentacarbonyl; Described long-chain amine is octadecylamine, lauryl amine; Described solvent is a vaccenic acid.
6. the preparation method of magnetic nano-substance as claimed in claim 4 is characterized in that: described step 2) the mixed dissolution material is added the thermal recovery sand-bath.
7. the preparation method of magnetic nano-substance as claimed in claim 4, it is characterized in that: described temperature remains on 330-350 ℃.
8. the preparation method of magnetic nano-substance as claimed in claim 4, it is characterized in that: described acetone solvent temperature is controlled at 45-50 ℃.
9. magnetic nano-substance as claimed in claim 1 is coated by capsule, is used for medicine and carries.
10. magnetic nano-substance as claimed in claim 1 is applied to magnetic fluid, magnetic resonance imaging, transducer and storage.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102579400A (en) * | 2012-03-26 | 2012-07-18 | 扬州大学 | Method for preparing microcapsules capable of controlling to release magnetic medicines in timing mode |
| CN104319054A (en) * | 2014-10-11 | 2015-01-28 | 昆明理工大学 | Manometer magnetofluid and application thereof to purification of pollutants |
| CN104361971A (en) * | 2014-10-07 | 2015-02-18 | 冯智勇 | Novel water-based magnetic fluid sealing material |
| CN105727599A (en) * | 2016-02-23 | 2016-07-06 | 同济大学 | Method for adopting magnetic nanometer particles for modifying demulsifying bacteria to reinforce lactescence demulsification |
| CN109731140A (en) * | 2018-12-27 | 2019-05-10 | 上海北陆医药科技有限公司 | A kind of long-acting gene expression cytoskeleton and preparation method thereof |
-
2009
- 2009-12-18 CN CN200910201399A patent/CN101710514A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102579400A (en) * | 2012-03-26 | 2012-07-18 | 扬州大学 | Method for preparing microcapsules capable of controlling to release magnetic medicines in timing mode |
| CN104361971A (en) * | 2014-10-07 | 2015-02-18 | 冯智勇 | Novel water-based magnetic fluid sealing material |
| CN104319054A (en) * | 2014-10-11 | 2015-01-28 | 昆明理工大学 | Manometer magnetofluid and application thereof to purification of pollutants |
| CN105727599A (en) * | 2016-02-23 | 2016-07-06 | 同济大学 | Method for adopting magnetic nanometer particles for modifying demulsifying bacteria to reinforce lactescence demulsification |
| CN105727599B (en) * | 2016-02-23 | 2017-11-07 | 同济大学 | The method that demulsifying bacteria is used to strengthen emulsion breakdown is modified using magnetic nano-particle |
| CN109731140A (en) * | 2018-12-27 | 2019-05-10 | 上海北陆医药科技有限公司 | A kind of long-acting gene expression cytoskeleton and preparation method thereof |
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Open date: 20100519 |