CN108346497A - A kind of magnetic nanoparticle and its flowing preparation method and system - Google Patents
A kind of magnetic nanoparticle and its flowing preparation method and system Download PDFInfo
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- CN108346497A CN108346497A CN201810087948.3A CN201810087948A CN108346497A CN 108346497 A CN108346497 A CN 108346497A CN 201810087948 A CN201810087948 A CN 201810087948A CN 108346497 A CN108346497 A CN 108346497A
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- H—ELECTRICITY
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract
The present invention discloses a kind of magnetic nanoparticle and its flowing preparation method and system, organo-metallic compound or metal salt compound presoma are dissolved in the small molecule with alkyl chain in solvent first in the preparation, form mixed reaction solution, then mixed reaction solution is passed through in flowing preparation system, utilize controllable temperature and pressure, it is reacted so that mixed reaction solution is in a supercritical state in the reactor, then passes through precipitation and isolated magnetic nanoparticle product.There is the magnetic nanoparticle obtained using the method for the present invention and flowing preparation system paramagnetism, superparamagnetism, ferrimagnetism or ferromagnetism, surface modification to have the small molecule with alkyl chain.Compared with traditional still reaction, the present invention flows synthetic technology and is greatly improved mass-and heat-transfer rate so that product particle crystallinity height, narrow particle size distribution.Automation control can be realized by flowing preparation system simultaneously so that the difference that product is respectively prepared between batch is smaller, reproducible, and can realize prepared by the magnanimity of nano particle by continuous sample introduction.
Description
Technical field
The present invention relates to materials chemistry, nano science and technical field of fine, especially a kind of magnetic nanoparticle
And its flow preparation method and system.
Background technology
Magnetic nanoparticle is due to its unique magnetic property, in magnetic resonance imaging, medicament transport and thermotherapy, bio-separation
Equal fields are widely applied, and especially SPIO nano particle and paramagnetic nanoparticle containing gadolinium are examined in tumour
Disconnected field shows wide potential applicability in clinical practice.However up to the present, almost all of magnetic Nano material passes through
Autoclave (flask) reaction synthesis, not only yield is small, but also difference is big between batch, magnetic Nano material repeatability and it is macro
Amount prepares the maximum bottleneck for having become its clinic conversion.
Flowing synthesis provides new selection as a kind of emerging preparation method for the synthesis of nano particle
(Angew.Chem.,Int.Ed.,2010,49,6268；Chem.Soc.Rev.,2010,39,1183.).Flowing synthesis system can
Reaction is set to carry out at higher temperatures and pressures, and this is difficult to realize in traditional still reaction bottle.Meanwhile it being substantially reduced
Reaction compartment advantageously reduce the localised waving of reaction condition.Most importantly, entire reaction process can be in automation, nothing
Stablize in the flow reactor of human interference and carry out, to realize prepared by continuous, the repetition of nano particle.Based on above-mentioned excellent
Point, flowing synthesis have been used for preparing semiconductor nanoparticle (CdSe, CdS) (Eur.Phys.J.D, 2009,52,15；
Chem.Commun., 2002,1136.), noble metal nano particles (Au, Ag) (Nano Lett., 2005,5,685.) and metal
Oxide nano particles (J.Mater.Chem., 2012,22,9041.).Though flowing synthesizing magnetic ferric oxide nanometer particle also has
Report (Adv.Funct.Mater., 2008,18,922；Nanoscale, 2013,5,2126.), but due to used in reaction
The defect of coprecipitation itself, the nano particle crystallinity that is prepared is poor, size distribution is wide, these deficiencies limit it significantly
Application.
Pyrolytic synthetic method has successfully prepared crystallinity height, size distribution that is, by pyrogenic metal organic precursor
It is narrow, composition is clear, magnetic nanoparticle that magnetic responsiveness is strong (J.Mater.Chem., 2009,19,6274；
J.Am.Chem.Soc.,2011,133,19512；J.Am.Chem.Soc.,2011,133,12664.).However, being based on this method
Research be concentrated mainly at present autoclave prepare on.Due to the complexity of high-temperature decomposition reaction, i.e., not only contain nano particle
Nucleating growth process, while there is also the pyrolysis processes of precursors, thus in preparation process reactor with
Heat and mass transfer process between reaction solution has extremely important influence, simultaneous reactions to the size of nano particle and size distribution
The random fluctuation of parameter is also easy to lead to particle size and the unpredictalbe variation of size distribution.In the above context, develop
Weakness of the new preparation method to overcome existing method to be not easy to repeat, to realizing magnetic nanoparticle in the wide of biomedical sector
General application has very important significance.
Invention content
The purpose of the present invention is to propose to a kind of magnetic nanoparticle and its flowing preparation methods and system, are based on pyrolytic
Method prepares the magnetic nanoparticle of crystallinity height, narrow particle size distribution using flowing synthetic technology, can realize magnetic Nano
The stabilization of grain is repeatable to be prepared, and the magnanimity preparation of nano particle can be realized by continuous sample introduction.
The technical solution that the present invention takes is：A kind of flowing preparation method of magnetic nanoparticle, including step：
Organo-metallic compound or metal salt compound presoma are dissolved in the small molecule with alkyl chain in solvent by S1,
Form reaction solution；
Reaction solution is passed through a flowing preparation system by S2, and the flowing preparation system includes that the controllable sample introduction of flow velocity is logical
The controllable reactor of road, temperature and pressure, cooling device and sample reception container, the sample intake passage, reactor, cooling dress
It sets and is sequentially communicated with sample reception container；
The fluid flow rate in sample intake passage is controlled, reaction solution is passed through in reactor by sample intake passage；
Control the temperature and pressure in reactor so that reaction solution is in a supercritical state in reactor to be obtained by the reaction
Magnetic nanoparticle sample；
Cooling treatment is carried out to the solution after reaction by cooling device, obtains reaction solution after cooling；
Reaction solution after cooling is passed through sample reception container；
S3, into reaction solution after cooling, addition precipitating reagent is precipitated, and then carries out isolated magnetic to sediment
Property nano particle.
The preparation method of the present invention is in use, can be by changing reaction condition, including the concentration of metallic precursor, band alkane
Concentration, reaction temperature, reaction pressure, residence time, reaction flow velocity, channel of reactor size of the small molecule of base chain etc., system
It is standby to obtain size and the different magnetic nanoparticle of size distribution.High temperature and pressure is controlled using reactor, at supercritical conditions
Nano particle is prepared, mass-and heat-transfer efficiency is improved, the nano particle of size evenly can be obtained.
It, can be before reaction solution enters flowing preparation system, by organo-metallic compound or metal salt chemical combination in step S1
Object presoma is dissolved in solvent together with the small molecule with alkyl chain, obtains mixed reaction solution.Organic gold in mixed reaction solution
Belong to a concentration of 0.001~1mol/L of compound or inorganic metal salt compound, preferred concentration is 0.01~0.1mol/L；Band alkane
A concentration of 0.001~the 2mol/L, preferably 0.01~0.6mol/L of the small molecule amine of base chain, small carboxylic acid molecules or small molecular alcohol.
Preferably, it flows in preparation system, sample intake passage size range is 0.05~10mm, and reaction solution flow control exists
0.02~1000mL/min, preferably 0.1~500mL/min；Reactor interior reaction temperature controls between 120~400 DEG C, preferably
180~300 DEG C, reaction pressure is controlled in 1~300 atmospheric pressure, preferably 3~100 atmospheric pressure；Mixed reaction solution is reacting
Residence time in device controls in 0.5~60min.
Further, step S1 further includes：By the way of ultrasound degassing or being passed through inert gas, to mixed reaction solution
Carry out deoxygenation.It deaerates according to ultrasound, time control is in 1~30min, according to being passed through inert gas mode, inert gas one
As selection nitrogen or argon gas, time control is in 5-120min.
It in step S2, flows in preparation system, the quantity of sample intake passage is multiple, between multiple sample intake passages and reactor
It is also communicated with a mixer, as another preparation method of mixed reaction solution, step S1 includes：
Organo-metallic compound or inorganic metal salt compounds precursors are dissolved in solvent, it is molten to obtain precursor by S11
Liquid；
S12 excludes the oxygen in precursor solution, small molecule and solvent with alkyl chain respectively；
Precursor solution after deoxygenation, the small molecule with alkyl chain and solvent it is logical to be each led into single sample introduction by S13
Road, and then enter in mixer and mix, form mixed reaction solution.
In step S11, a concentration of 0.001~10mol/L of precursor, preferred concentration is 0.01~1mol/L.Step S12
In, it deaerates according to ultrasound, time control is in 5~30min, and according to inert gas mode is passed through, inert gas is typically chosen
Nitrogen or argon gas, time control is in 10-120min.
The situation of the multiple sample intake passages of the present invention can be conveniently by regulating and controlling the flow velocity of reaction solution in each sample intake passage, and control is each
The concentration and ratio of reactant, to obtain different magnetic nanoparticles.Preferably, organic in reaction solution in reaction process
A concentration of 0.001~1mol/L of metallic compound or inorganic metal salt compound, preferred concentration are 0.01~0.1mol/L；Band
A concentration of 0~the 2mol/L, preferably 0.01~0.6mol/L of the small molecule amine of alkyl chain, small carboxylic acid molecules or small molecular alcohol；Respectively
Sample intake passage size range is 0.05~10mm；The reaction solution flow control of each sample intake passage is in 0.02~500mL/min, preferably
0.1~50mL/min；Reaction temperature in reactor controls between 80~350 DEG C, preferably 180~300 DEG C；It is anti-in reactor
Answer pressure control in 1~300 atmospheric pressure, preferably 3~100 atmospheric pressure；When stop of the mixed reaction solution in reactor
Between control in 0.5~60min.
Preferably, in step S1, the organo-metallic compound is to match containing transition metal or the organic of rare earth metal
Object is closed, such as iron, cobalt, nickel, manganese or lanthanide rare metal organic complex, ligand include acetylacetone,2,4-pentanedione, carbonyl, phenyl second
Acyl acetone, cyclopentadiene.The example of organo-metallic compound includes：Praseodynium iron, diacetyl acetone iron, iron pentacarbonyl,
Phenylacetyl acetone iron, diacetyl acetone manganese, phenylacetyl acetone manganese, diacetyl acetone nickel, nickel carbonyl, diacetyl acetone
Cobalt, cobalt octacarbonyl, praseodynium gadolinium, three cyclopentadiene gadoliniums, praseodynium dysprosium, acetylacetone,2,4-pentanedione holmium etc. are one or more
Mixing.
Preferably, in step S1, the metal salt compound is the salt containing transition metal and rare earth metal or its hydration
Object, such as the oleate of iron, cobalt, nickel, manganese or lanthanide rare metal, stearate, fatty acid salt, trifluoroacetate, grape acid
Salt, citrate, oxalates, chloride, sulfate, nitrate and its hydrate.The specific embodiment packet of metal salt compound
It includes but is not limited to：Iron oleate, ferric stearate, ferric acetate, ironic citrate, ferric oxalate, ferric trichloride, iron, four hydrations
Ferric trichloride, Iron(III) chloride hexahydrate, ferric nitrate, ferric sulfate, cobalt oleate, cobaltous octadecanate, cobalt acetate, citric acid cobalt, cobalt oxalate,
Cobalt decanoate, cobaltic chloride, manganese acetate, manganese oxalate, protochloride manganese, manganese nitrate, manganese sulfate, oleic acid gadolinium, stearic acid gadolinium, gadolinium acetate,
Gadolinium chloride, three chloride hydrate gadoliniums, six chloride hydrate gadoliniums, gadolinium nitrate, acetic acid dysprosium, dysprosium chloride, three chloride hydrate dysprosiums, six chloride hydrates
Dysprosium, dysprosium nitrate, acetic acid holmium, holmium chloride, three chloride hydrate holmiums, six chloride hydrate holmiums, holmium nitrate, acetic acid erbium, erbium chloride, three hydrations
Erbium chloride, six chloride hydrate erbiums, erbium nitrate, acetic acid thulium, thulium chloride, three hydrous thulium chlorides, six hydrous thulium chlorides, thulium nitrate etc..
Preferably, in step S1, the solvent is phenylate, methyl phenyl ethers anisole, dibenzyl ether, 1- octadecylenes, oleic acid, oleyl amine, three
The mixture of one or more of octylame, methanol, ethyl alcohol, isopropanol, n-butanol, hexamethylene, water or 2-Pyrrolidone, or on
State the derivative and analog of solvent.
Further, sediment is separated into step S3：Using precipitating reagent to sediment carry out wash cycles and
It detaches one or many.The purity for the magnetic nanoparticle product that so can be improved.The cycle-index of cleaning and separation can
It is 1~5 time.Magneto separate can be used to the separation of magnetic nanoparticle or centrifuge mode.
Preferably, in step S3, the precipitating reagent being added into the solution after reaction is 2~50 times of bodies of liquor capacity after reaction
Long-pending ethyl alcohol, methanol, acetone or their mixture.Separation is carried out to sediment and uses Magneto separate or centrifugal separation technology.
Invention additionally discloses a kind of magnetic nanoparticles, using the flowing preparation method preparation of aforementioned magnetic nanoparticle
At；Magnetic nanoparticle is magnetic transition metal and its oxide, magnetic lanthanide rare metal oxide, transition metal or rare earth
Metal-doped type magnetic oxide；More preferably iron, cobalt, nickel, manganese or iron cobalt nickel gadolinium terbium dysprosium holmium erbium thulium oxidation
Object；The grain size of magnetic nanoparticle is 1~100 nanometer；With paramagnetism, superparamagnetism, ferrimagnetism or ferromagnetism；It repaiies on surface
It is decorated with one or more in the small molecule amine with alkyl chain, small carboxylic acid molecules or small molecular alcohol；
Small molecule amine, small carboxylic acid molecules with alkyl chain and small molecular alcohol, CH2 unit numbers are 4~24 in alkyl chain.
Preferably 12~18, such as oleyl amine, lauryl amine, oleic acid, 1,2- dodecanediols, octadecyl alcolol etc..
Invention additionally discloses a kind of flowing preparation system, including controller and set gradually sample intake passage, reactor,
Cooler, counterbalance valve and sample reception container；Sample intake passage be equipped with sampling valve and sampling pump, reactor include heating unit,
Temperature feedback unit and pressure feedback unit；
Controller controls the work of sampling valve and sampling pump on sample intake passage, to control fluid flow direction reaction in sample intake passage
The time of device and flow；
Temperature feedback unit detects reactor temperature and is transmitted to controller, and controller is according to the temperature signal received
The operation for controlling heating unit, to control the reaction temperature in reactor；
Pressure feedback unit detects reactor pressure and is transmitted to controller, and controller is according to the pressure signal received
Counterbalance valve is controlled, to adjust the reaction pressure in reactor；
Controller controls the reaction temperature and reaction pressure in reactor so that the reaction solution in reactor is overcritical
It is reacted under state.
Active computer, industrial personal computer or microcontroller implementation can be used in above controller；Sampling valve and sampling pump can be adopted
With existing metering valve and metering pump, the control to metering valve and metering pump is the prior art；Pipe reaction can be used in reactor
Device, chip microreactor, material include Hastelloy, 316L stainless steels, glass, dimethyl silicone polymer (PDMS), ceramics
It is one or more, the mode of heating of reactor can be aluminium block heating or oil bath heating；Temperature feedback unit and pressure feedback list
Existing temperature sensor and pressure sensor can be respectively adopted in member.Cooler is used for the fluid after cooling reaction, can be used existing
Air cooling or water cooling class cooling device；One or more combinations can be used in counterbalance valve, can be carried for reaction system
Subject to required pressure.
Further, the quantity of sample intake passage is 2 or more, and sampling valve is respectively equipped on each sample intake passage and sampling pumps,
It is also communicated with a mixer between the outlet and reactor of multiple sample intake passages, the reagent that each sample intake passage is flowed out carries out
Mixing.Existing T-type, Y types or static mixer can be used in mixer, for being mixed to plurality of raw materials.
Advantageous effect
The magnetic nanoparticle of the present invention combines flowing preparation method to be prepared using flowing preparation system, flowing synthesis
System can react for raw material provide high temperature and pressure, and by control pressure and temperature, can make reaction can at supercritical conditions into
Row, substantially increases mass-and heat-transfer rate so that gained magnetic nanoparticle product crystallinity height, narrow particle size distribution；
Meanwhile flowing preparation system of the invention can realize automation control, stability prepared by optimization product and again
Renaturation so that the difference that product is respectively prepared between batch is smaller, and can realize prepared by the magnanimity of nano particle by continuous sample introduction.
Description of the drawings
Fig. 1 show the flowing synthesis system schematic diagram of the embodiment of the present invention 1；
Fig. 2 show the transmission electron microscope photo (A) of 3.0nm Fe3O4 nano particles obtained by 5-1 of the embodiment of the present invention and its
Histogram of particle size distribution (B)；
Fig. 3 show the X-ray diffraction spectrogram (A) of 3.0nm Fe3O4 nano particles obtained by 5-1 of the embodiment of the present invention and
PDF#88-0866 standard spectrograms (B)；
Fig. 4 show the hysteresis loop of 3.0nm Fe3O4 nano particles obtained by 5-1 of the embodiment of the present invention；
Fig. 5 show the transmission electron microscope photo (A) of 4.2nm Fe3O4 nano particles obtained by 5-2 of the embodiment of the present invention and its
Histogram of particle size distribution (B)；
Fig. 6 show the flowing synthesis system schematic diagram of the embodiment of the present invention 2；
Fig. 7 show the transmission electron microscope photo (A) and its grain of 8.6nmFe3O4 nano particles obtained by 5-3 of the embodiment of the present invention
Diameter distribution histogram (B)；
Fig. 8 show the transmission electron microscope photo (A) of 2.7nm ferric oxide nanometer particles obtained by 5-4 of the embodiment of the present invention and its
Histogram of particle size distribution (B)；
Fig. 9 show the transmission electron microscope photo (A) and its grain of 4.4nmGd2O3 nano particles obtained by 5-8 of the embodiment of the present invention
Diameter distribution histogram (B).
Specific implementation mode
It is further described below in conjunction with the drawings and specific embodiments.
Embodiment 1- flows preparation system
Refering to what is shown in Fig. 1, the flowing preparation system of the present embodiment, including controller and set gradually sample intake passage,
Reactor, cooler, counterbalance valve and sample reception container (sample bottle)；Sample intake passage is 1, and sample intake passage is equipped with sampling valve
It is pumped with sampling, reactor includes heating unit, temperature feedback unit and pressure feedback unit；
Controller controls the work of sampling valve and sampling pump on sample intake passage, to control fluid flow direction reaction in sample intake passage
The time of device and flow；
Temperature feedback unit detects reactor temperature and is transmitted to controller, and controller is according to the temperature signal received
The operation for controlling heating unit, to control the reaction temperature in reactor；
Pressure feedback unit detects reactor pressure and is transmitted to controller, and controller is according to the pressure signal received
Counterbalance valve is controlled, to adjust the reaction pressure in reactor.The temperature and pressure that reactor is controlled by controller, can make reaction
Reaction solution in device is in a supercritical state, prepares nano particle at supercritical conditions, is conducive to mass-and heat-transfer, obtains ruler
Very little nano particle evenly.
Active computer, industrial personal computer or microcontroller implementation can be used in above controller；Sampling valve and sampling pump can be adopted
With existing metering valve and metering pump, the control to metering valve and metering pump is the prior art；Pipe reaction can be used in reactor
Device, chip microreactor, material include Hastelloy, 316L stainless steels, glass, dimethyl silicone polymer (PDMS), ceramics
It is one or more, the mode of heating of reactor can be aluminium block heating or oil bath heating；Temperature feedback unit and pressure feedback list
Existing temperature sensor and pressure sensor can be respectively adopted in member.Cooler is used for the fluid after cooling reaction, can be used existing
Air cooling or water cooling class cooling device；One or more combinations can be used in counterbalance valve, can be carried for reaction system
Subject to required pressure.
Embodiment 2- flows preparation system
Refering to what is shown in Fig. 6, in the flowing preparation system of the present embodiment, the quantity of sample intake passage is multiple, each sample intake passage
On be respectively equipped with sampling valve and sampling pump, be also communicated with a mixer between the outlet and reactor of multiple sample intake passages, with
The reagent that each sample intake passage flows out is mixed.Existing T-type, Y types or static mixer can be used in mixer, for more
Kind raw material carries out being mixed to form mixed reaction solution, then is passed through in reactor and is reacted.
Setting and the embodiment 1 of controller, reactor, cooler, counterbalance valve and sample reception container in the present embodiment
It is identical.
Embodiment 3- flows preparation method
The flowing preparation method of the magnetic nanoparticle of the present embodiment, including step：
Organo-metallic compound or metal salt compound presoma are dissolved in the small molecule with alkyl chain in solvent by S1,
Form reaction solution；
Reaction solution is passed through a flowing preparation system by S2, and the flowing preparation system includes that the controllable sample introduction of flow velocity is logical
The controllable reactor of road, temperature and pressure, cooling device and sample reception container, the sample intake passage, reactor, cooling dress
It sets and is sequentially communicated with sample reception container；
The fluid flow rate in sample intake passage is controlled, reaction solution is passed through in reactor by sample intake passage；
Control the temperature and pressure in reactor so that reaction solution is in a supercritical state in reactor to be obtained by the reaction
Magnetic nanoparticle sample；
Cooling treatment is carried out to the solution after reaction by cooling device, obtains reaction solution after cooling；
Reaction solution after cooling is passed through sample reception container；
S3, into reaction solution after cooling, addition precipitating reagent is precipitated, and then carries out isolated magnetic to sediment
Property nano particle.
Step S1 further includes：By the way of ultrasound degassing or being passed through inert gas, deoxygenation is carried out to mixed reaction solution.
It deaerates according to ultrasound, time control is in 1~30min, and according to inert gas mode is passed through, inert gas is typically chosen nitrogen
Or argon gas, time control is in 5-120min.
Precipitating reagent is added in step S3 to be precipitated, is then cleaned to precipitating isolated magnetic nanoparticle,
And detach again, wash cycles and separating step are multiple, obtain magnetic nanoparticle product.The magnetism that so can be improved is received
The purity of rice grain product.The cycle-index of cleaning and separation can be 3~5 times.Magnetic can be used to the separation of magnetic nanoparticle
Separation centrifuges mode.
In step S3, the precipitating reagent being added into the solution after reaction is the second of 2~50 times of volumes of liquor capacity after reaction
Alcohol, methanol, acetone or their mixture.Separation is carried out to sediment and uses Magneto separate or centrifugal separation technology.
In step S1, a concentration of the 0.001 of organo-metallic compound or inorganic metal salt compound in mixed reaction solution~
1mol/L, preferred concentration are 0.01~0.1mol/L；The concentration of small molecule amine, small carboxylic acid molecules or small molecular alcohol with alkyl chain
For 0.001~2mol/L, preferably 0.01~0.6mol/L.
Flow in preparation system, sample intake passage size range is 0.05~10mm, reaction solution flow control 0.02~
1000mL/min, preferably 0.1~500mL/min；Reactor interior reaction temperature controls between 120~400 DEG C, preferably 180~
300 DEG C, reaction pressure is controlled in 1~300 atmospheric pressure, preferably 3~100 atmospheric pressure；Mixed reaction solution is in reactor
Residence time control in 0.5~60min.
In use, can be by changing reaction condition, including the concentration of metallic precursor, small molecule with alkyl chain is dense
Degree, reaction temperature, reaction pressure, residence time, reaction flow velocity, channel of reactor size etc., are prepared size and granularity
It is distributed different magnetic nanoparticles.
Embodiment 4- flows preparation method
It in step S2, flows in preparation system, the quantity of sample intake passage is multiple, refering to what is shown in Fig. 6, multiple sample intake passages
A mixer is also communicated between reactor, as another preparation method of mixed reaction solution, step S1 includes：
Organo-metallic compound or inorganic metal salt compounds precursors are dissolved in solvent, it is molten to obtain precursor by S11
Liquid；
S12 excludes the oxygen in precursor solution, small molecule and solvent with alkyl chain respectively；
Precursor solution after deoxygenation, the small molecule with alkyl chain and solvent it is logical to be each led into single sample introduction by S13
Road, and then enter in mixer and mix, form mixed reaction solution.
In step S11, a concentration of 0.001~10mol/L of precursor, preferred concentration is 0.01~1mol/L.Step S12
In, it deaerates according to ultrasound, time control is in 5~30min, and according to inert gas mode is passed through, inert gas is typically chosen
Nitrogen or argon gas, time control is in 10-120min.
After obtaining mixed reaction solution, step S2 to S3 and cooling in remaining steps reference implementation example 1, precipitation, separation,
Wash cycles separation and etc. content.
The situation of the multiple sample intake passages of the present embodiment can be conveniently by regulating and controlling the flow velocity of reaction solution in each sample intake passage, control
The concentration and ratio of each reactant, to obtain different magnetic nanoparticles.
In the present embodiment reaction process, organo-metallic compound or inorganic metal salt compound is a concentration of in reaction solution
0.001~1mol/L, preferred concentration are 0.01~0.1mol/L；Small molecule amine, small carboxylic acid molecules with alkyl chain or small molecule
A concentration of 0.001~2mol/L of alcohol, preferably 0.01~0.6mol/L；Each sample intake passage size range is 0.05~10mm；Respectively
The reaction solution flow control of sample intake passage is in 0.02~1000mL/min, preferably 0.1~500mL/min；Reaction in reactor
Temperature controls between 120~400 DEG C, preferably 180~300 DEG C；Reaction pressure is controlled in 1~300 atmospheric pressure in reactor,
It is preferred that 3~100 atmospheric pressure；Residence time of the mixed reaction solution in reactor controls in 0.5~60min.
In embodiment 3 and embodiment 4, organo-metallic compound described in step S1 is containing transition metal or rare earth gold
The organic coordination compound of category, such as iron, cobalt, nickel, manganese or lanthanide rare metal organic complex, ligand include acetylacetone,2,4-pentanedione, carbonyl
Base, phenylacetyl acetone, cyclopentadiene.The example of organo-metallic compound includes but not limited to：Praseodynium iron, diacetyl
Acetone iron, iron pentacarbonyl, phenylacetyl acetone iron, diacetyl acetone manganese, phenylacetyl acetone manganese, diacetyl acetone nickel, four carbonyls
Base nickel, diacetyl acetone cobalt, cobalt octacarbonyl, praseodynium gadolinium, three cyclopentadiene gadoliniums, praseodynium dysprosium, acetylacetone,2,4-pentanedione
Holmium etc..
Metal salt compound described in step S1 be the salt containing transition metal and rare earth metal or its hydrate, as iron,
Oleate, stearate, fatty acid salt, trifluoroacetate, grape hydrochlorate, the citric acid of cobalt, nickel, manganese or lanthanide rare metal
Salt, oxalates, chloride, sulfate, nitrate and its hydrate.The specific embodiment of metal salt compound includes but unlimited
In：Iron oleate, ferric stearate, ferric acetate, ironic citrate, ferric oxalate, ferric trichloride, iron, four iron chloride hexahydrates,
Iron(III) chloride hexahydrate, ferric nitrate, ferric sulfate, cobalt oleate, cobaltous octadecanate, cobalt acetate, citric acid cobalt, cobalt oxalate, cobalt decanoate, three
Cobalt chloride, manganese acetate, manganese oxalate, protochloride manganese, manganese nitrate, manganese sulfate, oleic acid gadolinium, stearic acid gadolinium, gadolinium acetate, gadolinium chloride, three
Chloride hydrate gadolinium, six chloride hydrate gadoliniums, gadolinium nitrate, acetic acid dysprosium, dysprosium chloride, three chloride hydrate dysprosiums, six chloride hydrate dysprosiums, nitric acid
Dysprosium, acetic acid holmium, holmium chloride, three chloride hydrate holmiums, six chloride hydrate holmiums, holmium nitrate, acetic acid erbium, erbium chloride, three chloride hydrate erbiums,
Six chloride hydrate erbiums, erbium nitrate, acetic acid thulium, thulium chloride, three hydrous thulium chlorides, six hydrous thulium chlorides, thulium nitrate etc.；
Solvent described in step S1 is phenylate, methyl phenyl ethers anisole, dibenzyl ether, 1- octadecylenes, oleic acid, oleyl amine, trioctylamine, first
The mixture of one or more of alcohol, ethyl alcohol, isopropanol, n-butanol, hexamethylene, water or 2-Pyrrolidone or above-mentioned solvent
Derivative and analog.
Embodiment 5- magnetic nanoparticles
Magnetic nanoparticle is prepared using the flowing preparation method of the magnetic nanoparticle of previous embodiment 3 or 4,
Grain size is 1~100 nanometer, has paramagnetism, superparamagnetism, ferrimagnetism or ferromagnetism；Surface modification has with the small of alkyl chain
It is one or more in molecular amine, small carboxylic acid molecules or small molecular alcohol.
Magnetic nanoparticle be iron, cobalt, nickel, manganese or iron cobalt nickel gadolinium terbium dysprosium holmium erbium thulium oxide.
Small molecule amine, small carboxylic acid molecules with alkyl chain and small molecular alcohol, CH2 unit numbers are 4~24 in alkyl chain.
Preferably 12~18, such as oleyl amine, lauryl amine, oleic acid, 1,2- dodecanediols, octadecyl alcolol etc..
Embodiment 5-1
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.71g ferric acetyl acetonades, 1.7g oleic acid, 1.6g oleyl amines, 2.0g 1,2- dodecanediols are dissolved in 20mL isopropyls
It is passed through nitrogen in alcohol, after stirring and carries out deoxygenation 20min, obtained mixed reaction solution is pumped into flowing synthesis system, reactor
Using tubular reactor, internal diameter 1.0mm, control reactor interior reaction temperature is 250 DEG C, residence time 20min, reaction
Flow velocity is 2mL/min, and reaction pressure is 30 atmospheric pressure.
Solution after reaction is after subcooler is cooled to room temperature, into sample reception bottle (sample reception container).
Go out the magnetic nanoparticle in reaction solution with acetone precipitation, acetone washing precipitation is used in combination 3 times, waits for its natural drying
Afterwards, magnetic nanoparticle is obtained.
Gained nano particle is dissolved in hexamethylene, obtained magnetic nanoparticle is carried out using transmission electron microscope (TEM)
Characterization, Fig. 2 are the transmission electron microscope photo (A) and its histogram of particle size distribution (B) of gained magnetic nanoparticle.It can by electromicroscopic photograph
Know, nano particle is almost spherical, and average grain diameter 3.0nm, size relative standard deviation is 10%, and property is good.Attached drawing 3 (A) is
X-ray diffraction (XRD) spectrogram of gained magnetic nanoparticle, gained nano particle crystallinity is high as seen from the figure, the spectrogram and attached
Fe3O4 standard spectrograms (PDF#88-0866), which meet, in Fig. 2 (B) preferably shows that prepared magnetic nanoparticle is received for Fe3O4
Rice grain.Attached drawing 4 is gained Fe3O4 magnetic nanoparticles respectively in the hysteresis loop of 1.8K and 300K, saturation magnetization
Respectively 42.7emu/g and 32.5emu/g shows that prepared nano particle magnetism is very strong, and has superparamagnetism in room temperature.
Embodiment 5-2
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.71g ferric acetyl acetonades, 1.7g oleic acid, 1.6g oleyl amines, 2.7g octadecyl alcolols are dissolved in 20mL toluene, will be obtained
Mixed reaction solution be pumped into flowing synthesis system, reactor uses tubular reactor, internal diameter 1.0mm, and control reaction is warm
Degree is 250 DEG C, and residence time of the reaction solution in reactor is 20min, and reaction flow velocity is 5mL/min, reaction pressure 50
A atmospheric pressure.Subsequent processes are identical as embodiment 5-1, and obtained magnetic Fe_3O_4 nano particle average grain diameter is 4.2nm,
Size relative standard deviation is 12%, and transmission electron microscope photo (A) and its histogram of particle size distribution (B) are as shown in Fig. 5.
Embodiment 5-3
With reference to figure 6, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 2, and implements
The flowing synthesis preparation method of example 4.
1.42g ferric acetyl acetonades are dissolved in 20mL methyl phenyl ethers anisoles, precursor solution is obtained.By pumping respectively by precursor
Solution, oleic acid, oleyl amine, methyl phenyl ethers anisole are pumped into single sample intake passage, and then carry out being mixed to get mixed reaction solution into mixer.
It controls sampling valve and sampling on sample intake passage to pump, to control flow velocity of the precursor solution in sample intake passage as 1mL/
The flow velocity of min, oleic acid are 0.38mL/min, and the flow velocity of oleyl amine is 0.39mL/min, and the flow velocity of methyl phenyl ethers anisole is 0.23mL/min.By
It is 2mL/min that this, which obtains mixed reaction solution overall flow rate,.Precursor solution, oleic acid, oleyl amine, methyl phenyl ethers anisole after mixer mixes, into
Enter reactor, used tubular reactor internal diameter is 1.0mm, and control reactor interior reaction temperature is 270 DEG C, and the residence time is
10min, reaction pressure are 10 atmospheric pressure.Subsequent processes are identical as embodiment 5-1, obtained magnetic Fe_3O_4 nanometer
Grain average grain diameter is 8.6nm, and size relative standard deviation is 13%, transmission electron microscope photo (A) and its histogram of particle size distribution
(B) as shown in Fig. 7.
Embodiment 5-4
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.71g ferric acetyl acetonades, 1.7g oleic acid, 1.6g oleyl amines are dissolved in 30mL isopropanols, ultrasound degassing deoxygenation
Obtained reaction solution is pumped into flowing synthesis system by 20min, and used tubular reactor internal diameter is 2.1mm, and reaction temperature is
260 DEG C, residence time 15min, reaction flow velocity is 8mL/min, and reaction pressure is 60 atmospheric pressure.Last handling process and implementation
Example 1 is identical, and obtained superparamag-netic iron oxide average grain diameter is 2.7nm, and size relative standard deviation is 7%, transmission
Electromicroscopic photograph (A) and its histogram of particle size distribution (B) are as shown in Fig. 8.
Embodiment 5-5
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
1.4g iron oleates, 3.4g oleic acid, 1.8g lauryl amines are dissolved in 30mL toluene, nitrogen deoxygenation 10 is passed through under stirring
Obtained reaction solution is pumped into flowing synthesis system by~20min, and used tubular reactor internal diameter is 2.1mm, reaction temperature
It it is 300 DEG C, residence time 10min, reaction flow velocity is 10mL/min, and reaction pressure is 60 atmospheric pressure.Last handling process with
Embodiment 1 is identical, and obtained superparamag-netic iron oxide average grain diameter is 6.2nm, and size relative standard deviation is 8%.
Embodiment 5-6
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.52g ferric acetyl acetonades, 1.2g oleic acid, 1.1g oleyl amines are dissolved in 30mL n-butanols, the reaction solution that will be obtained
It is pumped into flowing synthesis system, used tubular reactor internal diameter is 2.1mm, and reaction temperature is 240 DEG C, and the residence time is
3min, reaction flow velocity are 5mL/min, and reaction pressure is 50 atmospheric pressure.Last handling process is same as Example 1, obtained magnetic
Property ferric oxide nanometer particle average grain diameter be 3.3nm, size relative standard deviation be 10%.
Embodiment 5-7
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.5g cobalt oleates, 0.5g oleic acid, 0.4g oleyl amines are dissolved in 25mL phenylates, be passed through after stirring nitrogen deoxygenation 10~
Obtained reaction solution is pumped into flowing synthesis system by 20min, and used tubular reactor internal diameter is 1.0mm, and reaction temperature is
280 DEG C, residence time 30min, reaction flow velocity is 0.5mL/min, and reaction pressure is 30 atmospheric pressure.Last handling process and reality
Apply that example 1 is identical, obtained magnetic Co3O4 nano particles average grain diameter is 5.4nm, and size relative standard deviation is 12%.
Embodiment 5-8
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.89g acetylacetone,2,4-pentanediones gadolinium, 1.8g oleic acid, 1.6g oleyl amines are dissolved in 30mL1- octadecylenes, the reaction that will be obtained
Liquid pump becomes a mandarin dynamic synthesis system, and used tubular reactor internal diameter is 1.0mm, and reaction temperature is 320 DEG C, and the residence time is
60min, reaction flow velocity are 0.6mL/min, and reaction pressure is 30 atmospheric pressure.Last handling process is same as Example 1, obtains
Magnetic Gd2O3 nano particles average grain diameter be 4.4nm, size relative standard deviation be 9%, transmission electron microscope photo (A) and its
Histogram of particle size distribution (B) is as shown in Fig. 7.
Embodiment 5-9
With reference to figure 1, the preparation of the present embodiment magnetic nanoparticle uses the flowing synthesis system of embodiment 1, and implements
The flowing synthesis preparation method of example 3.
0.2g holmium chlorides, 2.0g oleic acid, 1.8g oleyl amines and 25mL1- octadecylenes are mixed, nitrogen deoxygenation is passed through under stirring
Obtained reaction solution is pumped into flowing synthesis system by 120min, and used tubular reactor internal diameter is 1.0mm, reaction temperature
It is 340 DEG C, residence time 30min, reacts flow velocity 0.5mL/min, reaction pressure is 40 atmospheric pressure.Last handling process and reality
Apply that example 1 is identical, obtained magnetic Ho2O3 nano particles average grain diameter is 5.4nm, and size relative standard deviation is 12%.
To sum up, the magnetic nanoparticle product that flowing preparation method is prepared is combined using present invention flowing preparation system
Crystallinity height, narrow particle size distribution；And the difference that product is respectively prepared between batch is smaller, and can realize nano particle by continuous sample introduction
Magnanimity prepare.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of flowing preparation method of magnetic nanoparticle, characterized in that including step：
Organo-metallic compound or metal salt compound presoma are dissolved in the small molecule with alkyl chain in solvent by S1, are formed
Reaction solution；
Reaction solution is passed through a flowing preparation system by S2, and the flowing preparation system includes the controllable sample intake passage of flow velocity, temperature
Degree and pressure controllable reactor, cooling device and sample reception container, the sample intake passage, reactor, cooling device and
Sample reception container is sequentially communicated；
The fluid flow rate in sample intake passage is controlled, reaction solution is passed through in reactor by sample intake passage；
Control the temperature and pressure in reactor so that reaction solution is in a supercritical state in reactor to be obtained by the reaction magnetism
Nanoparticle sample；
Cooling treatment is carried out to the solution after reaction by cooling device, obtains reaction solution after cooling；
Reaction solution after cooling is passed through sample reception container；
S3, into reaction solution after cooling, addition precipitating reagent is precipitated, and then carrying out isolated magnetism to sediment receives
Rice grain.
2. according to the method described in claim 1, it is characterized in that, in step S1, organo-metallic compound or nothing in reaction solution
A concentration of 0.001 ~ 1mol/L of machine metal salt compound；Small molecule amine, small carboxylic acid molecules or small molecular alcohol with alkyl chain
A concentration of 0.001 ~ 2mol/L；It flows in preparation system, sample intake passage size range is 0.05 ~ 10mm, and reaction flow velocity is
0.02 ~ 1000 mL/min, reactor interior reaction temperature are 120 ~ 400 DEG C, and reaction pressure is 1 ~ 300 atmospheric pressure, hybrid reaction
Residence time of the solution in reactor is 0.5 ~ 60 min.
3. method according to claim 1 or 2, characterized in that step S1 further includes：Inertia is deaerated or is passed through using ultrasound
The mode of gas carries out deoxygenation to mixed reaction solution；
A concentration of 0.01 ~ 0.1 mol/L of organo-metallic compound or inorganic metal salt compound in reaction solution；Band alkyl chain
Small molecule amine, small carboxylic acid molecules or small molecular alcohol a concentration of 0.01 ~ 0.6mol/L；It flows in preparation system, sample intake passage
Interior reaction flow velocity is 0.1 ~ 500 mL/min；Reactor interior reaction temperature is 180 ~ 300 DEG C, and reaction pressure is 3 ~ 100 big
Air pressure；It when deoxygenation, deaerates according to ultrasound, time control is in 1 ~ 30 min, according to being passed through inert gas mode, inert gas
Using nitrogen or argon gas, time control is in 5-120 min.
4. according to the method described in claim 1, it is characterized in that, in step S2, flow preparation system in sample intake passage quantity
To be multiple, a mixer is also communicated between multiple sample intake passages and reactor；Step S1 includes：
Organo-metallic compound or inorganic metal salt compounds precursors are dissolved in solvent, obtain precursor solution by S11；
S12 excludes the oxygen in precursor solution, small molecule and solvent with alkyl chain respectively；
Precursor solution after deoxygenation, the small molecule with alkyl chain and solvent are each led into single sample intake passage by S13, into
And enter in mixer and mix, form mixed reaction solution.
5. method according to claim 1 or 4, characterized in that in step S3, the precipitation that is added into the solution after reaction
Agent is ethyl alcohol, methanol, acetone or their mixture of 2 ~ 50 times of volumes of liquor capacity after reaction.
6. according to the method described in claim 5, it is characterized in that, sediment is separated into step S3：Utilize precipitating reagent
Wash cycles are carried out to sediment and are detached one or many.
7. method according to claim 1 or 4, characterized in that in step S1, the organo-metallic compound be containing
Cross the organic coordination compound of metal or rare earth metal；Metal salt compound is the salt containing transition metal and rare earth metal or its water
Close object；Solvent is phenylate, methyl phenyl ethers anisole, dibenzyl ether, 1- octadecylenes, oleic acid, oleyl amine, trioctylamine, methanol, ethyl alcohol, isopropanol, just
The derivative and analog of the mixture of one or more of butanol, hexamethylene, water or 2-Pyrrolidone or above-mentioned solvent.
8. a kind of magnetic nanoparticle, characterized in that using the flowing preparation side of the magnetic nanoparticle described in claim 1-7
Method is prepared；
Magnetic nanoparticle be magnetic transition metal and its oxide, magnetic lanthanide rare metal oxide and transition metal or
One kind in rare earth metal doping type magnetic oxide；
The grain size of magnetic nanoparticle is 1 ~ 100 nanometer；
With paramagnetism, superparamagnetism, ferrimagnetism or ferromagnetism；Surface modification has the small molecule amine with alkyl chain, small molecule
It is one or more in carboxylic acid or small molecular alcohol；Small molecule amine, small carboxylic acid molecules with alkyl chain and small molecular alcohol, alkyl chain
Middle CH2 unit numbers are 4 ~ 24.
9. a kind of flowing preparation system, characterized in that including controller and the sample intake passage set gradually, reactor, cooling
Device, counterbalance valve and sample reception container；Sample intake passage is equipped with sampling valve and sampling pumps, and reactor includes heating unit, temperature
Feedback unit and pressure feedback unit；
Controller controls the work of sampling valve and sampling pump on sample intake passage, and reactor is flowed to control fluid in sample intake passage
Time and flow；
Temperature feedback unit detects reactor temperature and is transmitted to controller, and controller is controlled according to the temperature signal received
The operation of heating unit, to control the reaction temperature in reactor；
Pressure feedback unit detects reactor pressure and is transmitted to controller, and controller is controlled according to the pressure signal received
Counterbalance valve, to adjust the reaction pressure in reactor；
Controller controls the reaction temperature and reaction pressure in reactor so that the reaction solution in reactor is in supercriticality
Under reacted.
10. flowing preparation system according to claim 9, characterized in that the quantity of sample intake passage be 2 or more, respectively into
It is respectively equipped with sampling valve on sample channel and sampling pumps, is also communicated with one between the outlet and reactor of multiple sample intake passages and mixes
Device mixes the reagent that each sample intake passage flows out.
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| CN1253513A (en) * | 1997-04-23 | 2000-05-17 | 株式会社荏原制作所 | Supercritical reaction apparatus and method |
| US20080233041A1 (en) * | 2006-08-10 | 2008-09-25 | Suk-Won Jang | Apparatus for trapping carbon nanotube and system and method for producing the carbon nanotube |
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