CN1549283A - Method for producing water dispersing magnetic nano particle with high-crystallinity - Google Patents
Method for producing water dispersing magnetic nano particle with high-crystallinity Download PDFInfo
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- CN1549283A CN1549283A CNA031362753A CN03136275A CN1549283A CN 1549283 A CN1549283 A CN 1549283A CN A031362753 A CNA031362753 A CN A031362753A CN 03136275 A CN03136275 A CN 03136275A CN 1549283 A CN1549283 A CN 1549283A
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- pyrrolidone
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- nanometer particles
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 8
- 239000002122 magnetic nanoparticle Substances 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 10
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDEBSAWXIHEMNF-UHFFFAOYSA-O cupferron Chemical compound [NH4+].O=NN([O-])C1=CC=CC=C1 GDEBSAWXIHEMNF-UHFFFAOYSA-O 0.000 claims abstract description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims abstract description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000151 polyglycol Polymers 0.000 claims abstract description 3
- 239000010695 polyglycol Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 50
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011553 magnetic fluid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PTPLXVHPKMTVIW-FPLPWBNLSA-N (Z)-hydroxyimino-oxido-phenylazanium Chemical compound O\N=[N+](/[O-])c1ccccc1 PTPLXVHPKMTVIW-FPLPWBNLSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- PRBXPAHXMGDVNQ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]acetic acid Chemical compound OCCOCCOCC(O)=O PRBXPAHXMGDVNQ-UHFFFAOYSA-N 0.000 claims description 2
- CTZBEEKYUWCPHV-UHFFFAOYSA-N C(C)(=O)C(C(C)=O)C(C)=O.[Fe] Chemical compound C(C)(=O)C(C(C)=O)C(C)=O.[Fe] CTZBEEKYUWCPHV-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000004781 supercooling Methods 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 claims 1
- 239000006249 magnetic particle Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 32
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 2
- 150000002506 iron compounds Chemical class 0.000 abstract description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 abstract description 2
- 239000011859 microparticle Substances 0.000 abstract 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- -1 iron pentacarbonyl Chemical class 0.000 abstract 1
- 159000000014 iron salts Chemical class 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000004043 responsiveness Effects 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000011953 bioanalysis Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 description 1
- ATLYKOUEGIGBCN-UHFFFAOYSA-N 1-ethylpyrrolidin-2-one 1-methylpyrrolidin-2-one Chemical compound C(C)N1C(CCC1)=O.CN1C(CCC1)=O ATLYKOUEGIGBCN-UHFFFAOYSA-N 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- FYZDLTIEHDHOGL-UHFFFAOYSA-N CC1CCC(=O)O1.C1(CCCO1)=O.CN(P(=O)(N(C)C)N(C)C)C Chemical compound CC1CCC(=O)O1.C1(CCCO1)=O.CN(P(=O)(N(C)C)N(C)C)C FYZDLTIEHDHOGL-UHFFFAOYSA-N 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241000605008 Spirillum Species 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 206010047400 Vibrio infections Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002405 nuclear magnetic resonance imaging agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
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- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Compounds Of Iron (AREA)
Abstract
The new method for preparing high crystallinity monodisperse water-soluble magnetic nano microparticles is characterized by that it selects the inorganic iron salts of anhydrous iron trichloride and iron chloride, etc. or metal organic iron compounds (such as iron pentacarbonyl, iron triacetylacetonate, iron biacetylacetonate, complex of cupferron and iron salt, iron octoate and ferric oxalate, etc.) as iron raw material, and utilizes high-temp. decomposition of them in high boiling point polar solvent (for example alpha-pyrrolidone and its derivatives (N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, etc.), N,N-dimethyl-2-imidazolone, hexametapol, gamma-butyrolactone and its derivative and low molecular weight (molecular weight M is less than or equal to 5000) polyglycol and its derivatives) to prepare magnetic nano microparticles. Said invention can adopts different iron raw materials and high boiling point polar solvents so as to obtain different types of magnetic nano microparticles (Fe, Fe2O3 and Fe3O4) with different sizes and crystallinities and different crystal structures.
Description
Technical field:
The present invention relates to a kind of method of utilizing single step reaction in high bp polar solvent, to prepare water dispersible magnetic nanometer particles with high-crystallinity, monodispersity.
Background technology:
Small-size effect, quantum size effect, skin effect etc. make nanoparticle (nanocrystal) have the magnetic property that conventional coarse grain material does not have, for example the magnetic property of iron and oxidate nano particulate thereof depends on the size and the degree of crystallinity of particulate consumingly, as Fe, γ-Fe
2O
3, Fe
3O
4The size of nanocrystal is during less than 5nm, 16nm, 20nm, and these particulates just embody superparamagnetism.Therefore by just can obtain having the nanoparticle material of different magnetic properties to the adjusting of particle size and degree of crystallinity.In numerous magnetic nanometer particles, research to iron and oxide thereof is the most extensive, and these particulates and composite material thereof exist widely in biomedical (magnetic resonance contrast agent, cell marking separation, DNA separation, medical diagnosis on disease and treatment, oncotherapy), chemical industry (catalyst, coating), military project (absorbing material), environmental protection various fields such as (recovery of heavy metal ion in the waste liquid) to be used.Yet the size of particulate, magnetic response character and water-solublely restricting the application of magnetic nanometer particles in above-mentioned various fields always.
For addressing the above problem, scientists has been explored the various methods that prepare magnetic nanometer particles by experiment, and in general, the method for preparing magnetic nanometer particles can be divided into physics method, bioanalysis and chemical method.In physical method, be main representative with the ball-milling method.Ball-milling method is that the particulate of micron or submicron order is ground through long-time (being generally a week or longer time), is distributed to then in the oil-based media (as kerosene) and gets.Although this method is convenient to operation, gained particle size distribution broad (nanoscale～micron order), length consuming time.Because magnetic nanometer particles is distributed widely in a lot of organisms, as various bacteriums (coccus, vibrios, spirillum, phycomycete), pigeon, honeybee, salmon, human body, therefore, bioanalysis is synthetic good method with biological compatibility magnetic nanoparticle.But organism (bacterium) is cultivated difficulty, and the particulate leaching process is loaded down with trivial details.In sum, physics method and bioanalysis shortcoming are outstanding, are unsuitable for scale and commercially produce magnetic nanometer particles, and chemical method becomes inevitable choice.
In the chemical method of synthesizing magnetic nanoparticle, can be divided into (being total to) precipitation method, micella (reverse micelle) method, ultrasonic decomposition method etc. again.(being total to) precipitation method are hydrolysis Fe under a certain pH value
3+, Fe
2+Or Fe
2+And Fe
3+Mixed solution prepare the method for ferric oxide nano particulate, pH value, microcrystallization degree that the size of this method gained particle size distribution broad, particulate and stability depend on system strongly are low, a little less than the magnetic responsiveness.Micella and reverse micelle method are the improvement to the precipitation method, the relative homogeneous of gained particle size, but also have above-mentioned shortcoming.The ultrasonic decomposition method is exactly to utilize the pyrolysis volatility organic metal compound of ultrasonic cavitation effect moment generation (as Fe (CO)
5) the preparation nanoparticle, this method gained particle size homogeneous, but degree of crystallinity is very low, magnetic responsiveness also very a little less than.
Summary of the invention:
The object of the present invention is to provide a kind of method that the pyrolysis iron containing compounds prepares the magnetic nanometer particles of single dispersion, high-crystallinity, strong magnetic responsiveness of using.
The invention provides a kind of method of the water-soluble magnetic nanoparticle of utilizing single step reaction to prepare in high bp polar solvent to have high-crystallinity, monodispersity (diameter is between 1 nanometer-100 nanometer), this method is applicable to that preparation has dispersibility or deliquescent Armco magnetic iron and oxide (γ-Fe thereof in water and intensive polar solvent
2O
3, Fe
3O
4) nanoparticle.
The present invention adopts the organic or inorganic compound of iron content as raw material, in 150～350 ℃, between preferred 180～300 ℃ it is added thermal response in high bp polar solvent, obtains magnetic nanometer particles then after supercooling, precipitation, separation.
The high-crystallinity that the present invention relates to, monodispersity, water miscible Armco magnetic iron and oxidate nano particulate preparation method thereof, its main feature include following two aspects:
(1) select for use high boiling polar solvent as reaction medium, high bp polar solvent mainly comprises alpha-pyrrolidone and derivative (N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone etc.) thereof, N, N-dimethyl-2-imidazolone, hexamethyl phosphoramide, gamma-butyrolacton and derivative thereof (4-methyl butyrolactone), low-molecular-weight (molecular weight M≤5000) polyethylene glycol and derivative (as diethylene glycol ether, triethylene glycol ether, tetraethylene glycol, poly glycol monomethyl ether, Polyethylene glycol dimethyl ether etc.) thereof, the molecular formula of above-mentioned various high bp polar solvent as follows
(alpha-pyrrolidone) (N-methyl 2-Pyrrolidone) (N-ethyl-2-pyrrolidone) (N, N-dimethyl-2-imidazolone)
(hexamethyl phosphoramide) (gamma-butyrolacton) (4-methyl butyrolactone)
(2) iron material of selecting wide material sources for use is as initiation material, and the iron material that is adopted among the present invention mainly comprises: the organic metal iron compound, as: praseodynium iron (Fe (acac)
3), diacetyl acetone iron (Fe (acac)
2), the complex compound of cupferron and molysite is (as FeCup
3, Cup:N-nitroso N-Phenylhydroxylamine), iron pentacarbonyl (Fe (CO)
5), iron octoate, ferric oxalate (Fe
2(C
2O
4)
35H
2O, FeC
2O
42H
2And inorganic molysite, O) etc. as anhydrous ferric trichloride, anhydrous ferrous chloride, iron chloride (FeCl
24H
2O, FeCl
36H
2O), ferric nitrate (Fe (NO
3)
39H
2O) or ferrous carbonate.
Its preparation process is as follows: iron material is dissolved in the high bp polar solvent, be mixed with 0.001mol/L～2mol/L, solution between preferred 0.01mol/L～0.5mol/L, under the anhydrous and oxygen-free condition in 150～350 ℃, heating reflux reaction is 10 minutes～10 hours between preferred 180～300 ℃, between preferred 10 minutes～4 hours, just can obtain the magnetic nanometer particles of 1 nanometer～100 nanometers.With common organic solvent (methyl alcohol, ethanol, isopropyl alcohol, butanols and acetone) precipitation, oven dry can obtain being easy to the magnetic nanometer particles dry powder that transports and store after the centrifugation with particulate solution.Gained dry powder also can be scattered in the distilled water once more and in the intensive polar solvent, form stable magnetic fluid.
Compare with traditional aqueous solution synthetic method, utilize that the resulting magnetic nanometer particles uniform particle diameter of the inventive method is controlled, degree of crystallinity is high, magnetic responsiveness is strong, and compare with the oil phase high-temperature decomposition with the ultrasonic decomposition method, the magnetic nanometer particles of this method gained has excellent water dispersible, and this provides huge convenience for magnetic nanometer particles is applied in biomedical aspect.In addition, the dispersibility of this method gained particulate dry powder greatly reduces the cost that stores and transport magnetic nanometer particles.In a word, the inventive method is convenient to operation, and is raw materials used cheap and easy to get, and gained magnetic nanometer particles advantage is outstanding, is suitable for scale and commercially produces, and has broad application prospects and market prospects.
Description of drawings:
Accompanying drawing 1: transmission electron microscope (TEM) photo of pressing case study on implementation 1～6 gained magnetic nanometer particles.
Accompanying drawing 2: the γ-Fe that presses the different crystallinity of case study on implementation 1～4 gained
2O
3The X-ray diffraction of magnetic nanometer particles (XRD) figure.
Accompanying drawing 3: the Fe that presses case study on implementation five gained
3O
4The X-ray diffraction of magnetic nanometer particles (XRD) figure.
Accompanying drawing 4: the schematic diagram behind magnetic nanometer particles dry powder water-soluble formation the stablizing magnetic fluid under the outside magnetic field effect.
Embodiment
Specific embodiment one:
Take by weighing the 0.43g ferric trichloride and be dissolved in the alpha-pyrrolidone of 50ml drying, heating reflux reaction 40 minutes is chilled to room temperature, and with a large amount of methyl alcohol (or ethanol, isopropyl alcohol, butanols, acetone) precipitation, centrifugation can obtain the precipitation of magnetic nanometer particles.As can be known, its particle diameter is 3nm by the TEM photo (Fig. 1 (A)) of gained particulate, and particle size distribution is narrower.Through X-ray diffraction analysis (XRD) (Fig. 2 (A)) as can be known the gained particulate be γ-Fe
2O
3, but the degree of crystallinity of particulate is lower, magnetic responsiveness relatively a little less than.
Specific embodiment two:
Take by weighing 0.31g Fe (CO)
5Be dissolved in the 50ml alpha-pyrrolidone, be heated to 244 ℃ of back flow reaction 60 minutes, all the other are operated all with embodiment one.Fig. 1 (B) is the TEM photo of gained particulate, and diameter of particle is 6nm as seen from the figure, and particle diameter is even.XRD (Fig. 2 (B)) shows that the gained particulate is γ-Fe
2O
3, and the degree of crystallinity of particulate is higher, and magnetic responsiveness is stronger.
Specific embodiment three:
Take by weighing 0.56g FeCup
3Be dissolved in the 100ml polyethylene glycol (M=400), heating reflux reaction 120 minutes, all the other are operated all with embodiment one.Fig. 1 (C) is the TEM photo of gained particulate, and diameter of particle is 10nm as seen from the figure, and particle diameter is even.XRD (Fig. 2 (C)) shows that the gained particulate also is γ-Fe
2O
3, diffraction maximum is stronger, and degree of crystallinity is higher, and magnetic responsiveness also strengthens.
Specific embodiment four:
Take by weighing 0.60g FeCup
3Be dissolved in the 60ml gamma-butyrolacton, 210 ℃ of heating reflux reactions 4 hours, all the other were operated all with embodiment one.The TEM photo shows that the gained diameter of particle is 11nm, and particle diameter is even.XRD (Fig. 2 (D)) shows that the gained particulate is γ-Fe
2O
3Particulate, and degree of crystallinity height, magnetic responsiveness is strong.
Specific embodiment five:
Take by weighing 0.18g Fe (acac)
3Be dissolved in the 60ml alpha-pyrrolidone, 250 ℃ of heating reflux reactions 30 minutes, be cooled to room temperature with a large amount of acetone precipitations, all the other are operated all with embodiment one.Fig. 1 (E) is the TEM photo of gained particulate, and diameter of particle is 8nm as seen from the figure, and particle diameter is even.XRD (Fig. 3) shows that the gained particulate is Fe
3O
4, the degree of crystallinity height of particulate, magnetic responsiveness is strong.
Specific embodiment six:
Take by weighing 0.20g Fe (CO)
5Be dissolved in the 60ml N-N-methyl-2-2-pyrrolidone N-, added thermal response 30 minutes at 150 ℃, be cooled to room temperature with a large amount of acetone precipitations, all the other are operated all with embodiment one.Fig. 1 (F) is the TEM photo of gained particulate, and diameter of particle is 5nm as seen from the figure, and particle diameter is even.XRD shows that the gained particulate is Fe, the degree of crystallinity height of particulate, and magnetic responsiveness is strong.
From above-mentioned each embodiment and remaining experiment, we can draw to draw a conclusion: (1) adopts different iron materials can obtain dissimilar (Fe, γ-Fe
2O
3, Fe
3O
4) magnetic nanometer particles, can obtain the di-iron trioxide nanoparticle as adopting inorganic molysite, adopt iron pentacarbonyl can obtain the iron nanoparticle, adopt ferric acetyl acetonade can obtain tri-iron tetroxide or di-iron trioxide nanoparticle; (2) control reaction temperature can obtain the magnetic nanometer particles of different crystalline textures and degree of crystallinity, and lower as the low gained microcrystallization degree of temperature, the high gained microcrystallization of temperature degree is higher; (3) remaining reaction condition such as reaction time and reactant concentration have considerable influence to the nanoparticle particle diameter, and be long as the reaction time, and the gained diameter of particle is bigger.
Claims (12)
1. magnetic nanometer particles preparation method comprises with iron containing compounds in 150～350 ℃, adding thermal response between preferred 180～300 ℃ as raw material in high bp polar solvent, obtains magnetic nanometer particles then after supercooling, precipitation, separation.
2. according to the preparation method of claim 1, wherein said iron containing compounds is selected from down the material of group for one or more: inorganic molysite and metal organoiron compound.
3. according to the preparation method of claim 2, wherein said inorganic molysite is anhydrous ferric trichloride, Iron(III) chloride hexahydrate, four hydration ferrous chloride, nine nitric hydrate iron or ferrous carbonates.
4. according to the preparation method of claim 2, wherein said metal organoiron compound is selected from the complex compound such as the FeCup of iron pentacarbonyl, diacetyl acetone iron, praseodynium iron, cupferron and molysite
3, Cup:N-nitroso N-Phenylhydroxylamine, iron octoate, ferric oxalate.
5. according to the preparation method of claim 1, wherein said high bp polar solvent is selected from down one or more in the group: alpha-pyrrolidone and derivative thereof, N, N-dimethyl-2-imidazolone, hexamethyl phosphoramide, gamma-butyrolacton and derivative, low molecular poly and derivative thereof.
6. according to the preparation method of claim 5, wherein said alpha-pyrrolidone derivative is N-N-methyl-2-2-pyrrolidone N-or N-ethyl-2-pyrrolidone, and low molecular poly and derivative thereof comprise diethylene glycol ether, triethylene glycol ether, tetraethylene glycol, poly glycol monomethyl ether, Polyethylene glycol dimethyl ether.
7. according to the preparation method of claim 1, reactant concentration is controlled between 0.001mol/L～2mol/L, between preferred 0.01mol/L～0.5mol/L.
8. according to the preparation method of claim 1, adopt methyl alcohol, ethanol, isopropyl alcohol, butanols or acetone precipitation magnetic particle.
9. according to the preparation method of claim 1, wherein the reaction time is 10 minutes～10 hours, between preferred 10 minutes～4 hours.
10. according to the preparation method of claim 1, the diameter of gained magnetic nanometer particles is between 1 nanometer～100 nanometers.
11. according to the preparation method of claim 1, wherein said magnetic nanometer particles is Fe, Fe
2O
3, or Fe
3O
4Magnetic nanometer particles.
12. according to the preparation method of claim 1, gained magnetic nanometer particles dry powder can dissolve once more or be distributed in the distilled water and the part intensive polar solvent in, form stable magnetic fluid.
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| CN101178961B (en) * | 2006-11-10 | 2011-02-09 | 北京万德高科技发展有限公司 | Water soluble magnetic nanometer crystal with high dissolvability and method of producing the same |
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| CN102616735A (en) * | 2012-04-06 | 2012-08-01 | 中国科学院化学研究所 | Single-formula biocompatible magnetic nanometer crystal size controlling preparation technology |
| CN111257408A (en) * | 2020-02-18 | 2020-06-09 | 广东省特种设备检测研究院珠海检测院 | Effervescent tablet containing nano magnetic powder and application thereof |
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