CN100383895C - Hydrophobic nano particles and process for preparing dispersion liquid thereof - Google Patents
Hydrophobic nano particles and process for preparing dispersion liquid thereof Download PDFInfo
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- CN100383895C CN100383895C CNB2004100515733A CN200410051573A CN100383895C CN 100383895 C CN100383895 C CN 100383895C CN B2004100515733 A CNB2004100515733 A CN B2004100515733A CN 200410051573 A CN200410051573 A CN 200410051573A CN 100383895 C CN100383895 C CN 100383895C
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- 239000007788 liquid Substances 0.000 title claims abstract description 34
- 239000006185 dispersion Substances 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 title claims description 24
- 230000002209 hydrophobic effect Effects 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000004094 surface-active agent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical group CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 150000002596 lactones Chemical group 0.000 claims 1
- 230000005415 magnetization Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000002356 single layer Substances 0.000 abstract 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000012454 non-polar solvent Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 125000004185 ester group Chemical group 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010038848 Retinal detachment Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000004264 retinal detachment Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The present invention relates to an esterophilic magnetic nanometer particle and a preparation technique of a dispersion liquid thereof. The preparation process comprises magnetic nanometer particle preparation, particle esterophilic reaction and particle dispersion in a non-polar solvent. Iron salt and aqueous alkali are mixed for carrying out reaction to prepare magnetic nanometer particles; the prepared nanometer particles are mixed with a surface active agent of more than two times of full monolayer amount, and the pH value of the mixed liquid is regulated to that esterophilic reaction is carried out; then, acid is added to regulate the pH value to an acidity range, and the separated nanometer particle precipitate is orderly washed with acid water and pure water; finally, the nanometer particle precipitate is dried. The surface of the esterophilic magnetic nanometer particle prepared by the preparation technique is fully covered with the monolayer surface active agent, which has a complete non-polar esterophilic surface and can be directly dispersed in a non-polar oil ester solvent, and the magnetic nanometer particle dispersion liquid with uniform and stable performance, high density, high saturation magnetization and strong magnetic flow performance can be obtained.
Description
Technical field
The present invention relates to the technology of preparing of a kind of close ester magnetic nanometer particles and dispersion liquid thereof.
Technical background
Nanoparticle is meant that size is in the particulate of (being nanoscale) in 1～100nm scope.Particulate under this class nanoscale has unique advantage: specific area is big, magnetic particle has the magnetic controllability, can select various modification process to carry out microparticle surfaces design etc., its liquid shows the rheological property that is different from conventional liq, thereby at machinery, building, precision instrument is made, medical diagnosis, pharmacy, coating, dyestuff, catalyst, ink, has special purposes in the multiple sciemtifec and technical sphere such as magnetic storage medium, wherein, be used for the controlled release drug carrier, the magnetocaloric effect treatment, the mangneto vascular occlusive agent, the magnetic resonance image (MRI) contrast-enhancing agents, the retinal detachment therapeutic agent, the research of magnetic carrier of separating etc., in recent years in materialogy, chemistry and physics, in the interdisciplinary fields such as life subject, show application prospects.
Chemical precipitation method is the main method of a large amount of magnetic nano-particles of preparation.For with these microparticulate in non-polar organic solvent, must carry out close esterification treatment to microparticle surfaces.So far have some and solve the patent and the documents and materials of this class technical problem.For example, United States Patent (USP) 3214278 (Hanneman, October nineteen sixty-five), 3531413 (Rosensweig, in September, 1970), 3017538 (Rosensweig, in November, 1975), 4430239 (Wyman, in February, 1984), RE32573 (Furumura, in January, 1988), 5411730 (Kirpotin, Mays nineteen ninety-five); Chinese patent 011051167, ZL01126182.X, 03130423.0 etc.These patents also respectively have limitation magnetic nanometer particles preparation and technical the having their own characteristics each of surperficial close esterification treatment.The present invention solves magnetic nanometer particles parent ester performance emphatically, make its can higher concentration, more even, stably be scattered in the non-polar organic solvent.
Even, the stable and high concentration of parent's ester magnetic nanometer particles in liquid phase medium (nonpolar organic media) disperseed, and is the precondition of many important application.Can the degree of scatter of magnetic nanometer particles in non-polar solven (as oil) except that the character that depends on selected surfactant (as the HLB value), form on magnetic nanometer particles surface with this surfactant also that completely to cover individual layer directly related.If the magnetic nanometer particles surface coverage a complete surfactant individual layer, formed new surface is exactly close ester, can produce strong interaction with nonpolar organic media, constitute the full solvated layer that covers, and evenly, stable, be scattered in this solvent to high concentration.But, according to the existing close esterification treatment method that the magnetic nanometer particles surface is carried out, the incomplete often individual layer that forms on the magnetic nanometer particles surface, or has individual layer (Fig. 1 of part bilayer, Fig. 2), either way reduced the dispersibility of magnetic nano-particle in nonpolar organic media because of the existence that the part water-wetted surface is arranged.The solution of this problem has become the critical problem that improves close ester nanoparticle and dispersing liquid quality and performance.
Summary of the invention
Purpose of the present invention, exactly in order to solve described problem, simplify the preparation technology of close ester magnetic nanometer particles and dispersing liquid thereof, realize its in non-polar solven evenly, stable, high concentration disperses, to obtain to have the stabilized magnetic liquid of high saturation and magnetic intensity and strong magnetorheological performance.
The present invention proposes the technology of preparing of a kind of close ester magnetic nanometer particles and dispersion liquid thereof, by magnetic nanometer particles preparation, microparticle surfaces parent's esterification treatment and the dispersion process of particulate in non-polar solven, prepare close ester magnetic nanometer particles and dispersing liquid thereof.Prepared close ester magnetic nanometer particles surface has the individual layer surfactant of full covering, and that its dispersing liquid has is uniform and stable, the performance of high density, high saturation and magnetic intensity and strong magnetorheological.
The present invention realizes by following principle: at first under alkali condition, with prepared magnetic nanometer particles and surfactant reaction, the double-layer surface-active agent that forms full covering at nano-particle surface (is seen Fig. 3, A, B), make it have surface hydrophilicity, and be scattered in (Fig. 3) in the aqueous solution; The nanoparticle that will completely cover double-layer surface-active agent is again separated, washes clean, be scattered in the aqueous solution once again, this dispersion liquid of acidifying, be covered in the outermost surfactant in magnetic nanometer particles surface and (see Fig. 3, B) split away off because of acidifying forms free acid, stay the close ester magnetic nanometer particles that has full covering surfaces activating agent individual layer and from water, separate out; Through separation, washing, drying, the magnetic nanometer particles that obtains has the surfactant of full individual layer because of its surface coverage, and present the strongest hydrophobic oil-wet behavior, can be scattered in well in the non-polar solven, form close ester nanoparticle and dispersing liquid (Fig. 4) thereof stable, even, high concentration.
Embodiment of the present invention are: make molysite and aqueous slkali finish hybrid reaction in 0.1～120 minute, add 5～1000 times of amounts, 1～30 ℃ water, 100～40000rpm stirred 1～10 hour down, obtained magnetic nanometer particles (Fe3O4); The magnetic nanometer particles that centrifugation is prepared, with pure water washing 1～3 time, 100～10000rpm stirring adds the aqueous solution of pH8～12 down and mixes with surfactant, heating, stirring reaction are 5～60 minutes under 40～95 ℃, be cooled to room temperature, regulate pH to 2～6, separate the magnetic nanometer particles precipitation of separating out, finish the close esterification process of nanoparticle; Particulate deposits is washed 1～3 time with the acid water of pH 2～6, again with pure water washing 3～5 times, drying.The close ester magnetic nanometer particles precipitation of preparation can directly be scattered in the non-polar solven thus, forms close ester nano-dispersed liquid.
Said molysite can be high ferro and ferrous sulfate, hydrochloride, nitrate, perchlorate etc.
Said aqueous slkali can be NaOH, potassium hydroxide, ammoniacal liquor, tetramethylammonium hydroxide etc.
Said magnetic nanometer particles also goes for the nanoparticle (as carbonate, silicate, sulfate, phosphate etc.) that methods such as other physics, chemistry prepare.
Said surfactant, can be a kind of contain 10 above carbon atoms and above polar group (as-COOH ,-OH ,-SO
3Deng) compound and acid, salt or lactone form, as oleate, phosphate, fatty acid methyl ester α-sodium sulfonate (MES) etc.
Said non-polar solven can be kerosene, paraffin oil, olive oil, diffusion pump oil, chloromethanes, aromatic hydrocarbon solvent, polystyrene monomers, polyphenylene oxide, dimethicone, diethyl silicone oil etc.
Adopt this method, can prepare various close ester magnetic nanometer particles and dispersion liquid thereof.As close ester γ-Fe
2O
3,
1M
(1-x) 2M
xFe
2O
4(in the formula
1M and
2M represents transition metals such as two valency iron, cobalt, nickel, zinc, manganese respectively) etc.Prepared close ester magnetic nanometer particles surface has the individual layer surfactant of full covering, performances such as that its dispersing liquid has is uniform and stable, high density, high saturation and magnetic intensity and strong magnetorheological.
Adopt the magnetic nanometer particles and the dispersing liquid thereof of this method preparation, the particle diameter of its nanoparticle can reach below the 10nm, and granularity evenly distributes in ± 2nm scope, and crystal formation is definite, has the good hydrophilic dispersing characteristic.The surface energy of this particulate forms static and aquation screen, can be scattered in the aqueous media by high-concentration stable, and the magnetic liquid of formation has high magnetorheological.The magnetic liquid of Xing Chenging has the advantages that density value is big, saturation magnetization is high, magnetic susceptibility is strong thus.
Description of drawings
Fig. 1 nano-particle surface partly covers the schematic diagram of individual layer surfactant
The close ester group of A1 surfactant
The hydrophilic group of A2 surfactant
The C magnetic nanometer particles
D is the polar surfaces of the magnetic nanometer particles of covering surfaces activating agent not
E partly covers the close ester surface of double-layer surface-active agent
Fig. 2 nano-particle surface partly covers the schematic diagram of double-layer surface-active agent
A1 internal layer surfactant A
*Close ester group
B1 superficies activating agent B
*Close ester group
The hydrophilic group of A2 internal layer surfactant A
The hydrophilic group of B2 superficies activating agent B
The C magnetic nanometer particles
E is covered with the close ester surface of individual layer surfactant
F partly covers the water-wetted surface of double-layer surface-active agent
(
*A, B are same surfactants herein, are to distinguish the difference of its present position with different symbols)
Fig. 3 nano-particle surface completely covers the schematic diagram of double-layer surface-active agent
The close ester group of A1 surfactant A
The close ester group of B1 surfactant B
The hydrophilic group of A2 surfactant A
The hydrophilic group of B2 surfactant B
The C magnetic nanometer particles
The G polar solvent
Fig. 4 nano-particle surface completely covers the schematic diagram of individual layer surfactant
The close ester group of A1 surfactant A
The hydrophilic group of A2 surfactant A
The C magnetic nanometer particles
The H non-polar solven
Fig. 5 magnetic Nano fluid film is the microscope image under the magnetic field externally: (* 50000)
When A, the magnetic line of force are parallel to the liquid film surface
B, the magnetic line of force is perpendicular to liquid film when surface
Specific embodiment
Below in conjunction with embodiment, further describe content of the present invention, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
With 0.2moL/L FeCL
2With 0.4moL/L FeCL
3Mix with concentrated ammonia liquor, react after 1 minute, add 200 times of amounts, 10 ℃ water, 10000rpm stirred 2.5 hours down; Separate prepared Fe
3O
4Nanoparticle, with pure water washing 2 times, 4000rpm stirs the aqueous solution that adds pH 8.4 down, mixed with the enuatrol of 2.5 times of amounts of calculation under 4000rpm stirs then, under 85 ℃, added thermal response 20 minutes, be cooled to 25 ℃, regulate pH to 5.2, separate the magnetic nanometer particles precipitation of separating out with the method that applies the external magnetic field; Precipitation is with the acid water of pH 4.2 washing 1 time, again with dry after the pure water washing 3 times; Dried close ester Fe
3O
4Particulate deposits directly is scattered in the diffusion pump oil, forms close ester Fe
3O
4The magnetic Nano dispersing liquid.Magnetic fluid film by the preparation of this dispersing liquid externally can show very strong magnetorheological (Fig. 5) down in magnetic field, when the magnetic line of force is parallel to the liquid film surface, the nanoparticle in the liquid film all be arranged in parallel (Fig. 5, A); When the magnetic line of force perpendicular to liquid film when surface, in the liquid film arrangement of nanoparticle also thereupon conversion direction (Fig. 5, B).
Prepared Fe
3O
4Magnetic nanometer particles dispersion liquid performance sees Table 1.
Table 1Fe
3O
4The magnetic nanometer particles dispersion liquid
Embodiment 2
With the Fe for preparing
3O
4Nanoparticle is separated under 10000rpm, with pure water washing 2 times, 4000rpm stirs the aqueous solution that adds pH 9.2 down, under stirring, mixes 6000rpm then with the octyl phosphate of 2.3 times of amounts, adding thermal response under 90 ℃ after 15 minutes, be cooled to 25 ℃, regulate pH to 4.6, separate the magnetic nanometer particles precipitation of separating out with the method that applies the external magnetic field; Precipitation is with the acid water of pH 5.2 washing 1 time, again with dry after the pure water washing 3 times; Dried close ester Fe
3O
4The magnetic particle precipitation directly is scattered in the kerosene, obtains close ester Fe
30
4The magnetic Nano dispersing liquid.
Embodiment 3
With the Co for preparing
xNi
(1-x)Fe
2O
4Nanoparticle is separated with the method that applies magnetic field, with pure water washing 3 times, the aqueous solution that under 6000rpm stirs, adds pH 10.5, under stirring, mixes 5000rpm then with the enuatrol of 3 times of amounts, adding thermal response under 70 ℃ after 40 minutes, be cooled to 25 ℃, regulate pH to 5.3, separate the magnetic nanometer particles precipitation of separating out with the method that applies the external magnetic field; Precipitation is with the acid water of pH 4.8 washing 1 time, again with dry after the pure water washing 3 times; Dried close ester Co
xNi
(1-x)Fe
2O
4The magnetic particle precipitation directly is scattered in the olive oil, obtains close ester Co
xNi
(1-x)Fe
2O
4The magnetic Nano dispersing liquid.
Claims (9)
1. the preparation method of a close ester magnetic nanometer particles is characterized in that this method comprises the steps:
A at first under alkali condition, with magnetic nanometer particles and surfactant reaction, forms the double-layer surface-active agent of full covering at nano-particle surface;
The nanoparticle of the double-layer surface-active agent that b will completely cover is again separated, be scattered in the aqueous solution once again, the mode of this aqueous dispersion of employing acidifying is removed the superficies activating agent of nano-particle surface, stays the lipophilicity magnetic nanometer particles that has full covering individual layer surfactant and separates out from water;
C obtains the lipophilicity magnetic nanometer particles through separation, washing, drying.
2. the preparation method of close ester magnetic nanometer particles as claimed in claim 1, it is characterized in that: make molysite and high concentration alkali solution in 0.1～120 minute, finish mixed reaction, add 5～1000 times of amounts, 1～30 ℃ water, 100～40000rpm stirred 1～10 hour down; Separate prepared magnetic nanometer particles, can obtain the needed magnetic nanometer particles of a step.
3. the preparation method of close ester magnetic nanometer particles as claimed in claim 1, it is characterized in that in step a, with pure water washing 1～3 time, 100～10000rpm stirs the aqueous solution that adds pH8～12 down, under 100～10000rpm stirs with more than the full surfactant that covers double-deck amount, mix, can obtain the double-layer surface-active agent nanoparticle of full covering.
4. the preparation method of close ester magnetic nanometer particles as claimed in claim 3, the consumption that it is characterized in that surfactant is 2.3-3 a times of nanoparticle consumption.
5. the preparation method of close ester magnetic nanometer particles as claimed in claim 1, it is characterized in that in step b, under 40～95 ℃, added thermal response 5～60 minutes, be scattered in the aqueous solution until magnetic nanometer particles, be cooled to room temperature, regulate pH to 2～6, separate the magnetic nanometer particles precipitation of separating out; In step c, the acid water washing precipitation of usefulness pH 2～6 1～3 time is again with pure water washing 3～5 times; Obtain close ester magnetic nanometer particles after the drying.
6. the preparation method of close ester magnetic nanometer particles as claimed in claim 1 is characterized in that: surfactant is a kind of nonpolar part and the compound of an above polar group and compound of acid, salt or lactone form thereof that contains 10 above carbon atoms.
7. the preparation method of close ester magnetic nanometer particles as claimed in claim 6 is characterized in that above-mentioned surfactant is oleate, phosphate.
8. as the preparation method of claim 1 or 4 described close ester magnetic nanometer particles, it is characterized in that: dried close ester magnetic nanometer particles precipitation directly is scattered in the non-polar solven, forms the nonpolar dispersion liquid of magnetic nanometer particles.
9. the preparation method of close ester magnetic nanometer particles as claimed in claim 8 is characterized in that: non-polar solven is any one in kerosene, paraffin oil, olive oil, diffusion pump oil, chloromethanes, aromatic hydrocarbon solvent, styrene monomer, polyphenylene oxide, dimethicone, the diethyl silicone oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100515733A CN100383895C (en) | 2004-09-22 | 2004-09-22 | Hydrophobic nano particles and process for preparing dispersion liquid thereof |
Applications Claiming Priority (1)
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| CN1258372A (en) * | 1997-04-04 | 2000-06-28 | 振义·罗克斯·洪 | Magnetic Fluid Thin Film Displays and Monochromatic Optical Switches |
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| CN1258372A (en) * | 1997-04-04 | 2000-06-28 | 振义·罗克斯·洪 | Magnetic Fluid Thin Film Displays and Monochromatic Optical Switches |
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