CN101783217A - Method for preparing silicon dioxide-coated magnetic microspheres - Google Patents
Method for preparing silicon dioxide-coated magnetic microspheres Download PDFInfo
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- CN101783217A CN101783217A CN 200910200743 CN200910200743A CN101783217A CN 101783217 A CN101783217 A CN 101783217A CN 200910200743 CN200910200743 CN 200910200743 CN 200910200743 A CN200910200743 A CN 200910200743A CN 101783217 A CN101783217 A CN 101783217A
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Abstract
The invention discloses a method for preparing silicon dioxide-coated magnetic microspheres, which belongs to the technical field of nano-magnetic materials. In the method, the characteristic that nanoparticles are easily arranged on a two-phase solution interface is utilized to form oil-in-water emulsion or microemulsion which is stabilized by oil-soluble magnetic nanoparticles and the hydrolysis of tetraethyl orthosilicate is further produced on the surfaces of droplets, so that a silicon dioxide-coated layer is formed. The method has the advantages of no need of using any surfactant, simple reaction operation process and short reaction time; particle diameters of the coated magnetic microspheres are 50 to 400nm; and the magnetic content of the microspheres can be simply controlled at the same time when the particle diameters of the magnetic microspheres are controlled.
Description
Technical field
What the present invention relates to is a kind of method of nano magnetic material technical field, specifically is a kind of preparation method with magnetic microsphere of coated with silica.
Background technology
Superparamagnetic nano particle is having a wide range of applications aspect cell separation, thermotherapy, drug targeting conveying and the magnetic resonance detection owing to its no remanent magnetism, zero coercitive characteristic.In present existing preparation method, the oil-soluble magnetic nanoparticle that reaction makes in the oil phase system is all will be significantly better than react the water-soluble magnetic nano particle that makes in aqueous phase system on pattern, uniform particle diameter and degree of crystallinity.But, be further in the biomedical sector practical application, need usually at first the oil-soluble magnetic nanoparticle is converted into water-soluble, and again in its finishing specific functional group be used for and the biomolecule coupling.Silicon dioxide is owing to its excellent biological compatibility and be easy to the surface functional group modification, has a wide range of applications in fields such as bio-medical, clinical diagnosis and immunoassays, often is used to the surface coating layer as nano particle.
For the method at oil-soluble magnetic nanoparticle surface coated silica layer, the method for bibliographical information mainly is divided into two classes at present: the one, and use surfactant that hydrophilic modification is carried out on the surface of oil-soluble magnetic nanoparticle earlier, and then pass through
The method coated silica.Surfactant commonly used has: CTAB, lauryl sodium sulfate etc.The 2nd, form earlier water in oil reverse micro emulsion, the oil-soluble magnetic nanoparticle is gone into water through ligand exchange is laggard.Pass through equally again
Method, in the water drop that is limited size, the coated silica layer.But two above class methods all exist certain deficiency, use surfactant to carry out performing hydrophilic modification on surface in advance such as needs, and the reaction time is long etc.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method with magnetic microsphere of coated with silica is provided, utilize nano particle to be easy on the two phase liquid interface, arrange, thereby reduce the characteristic of interface energy, formation is by oil-soluble magnetic nanoparticle stable O/w emulsion or microemulsion, formation is by the oil phase drop of magnetic nanoparticle dense distribution, and the hydrolysis of positive tetraethyl orthosilicate further takes place by the surface at this drop, forms the coated with silica layer.The present invention does not need to use any surfactant, and the operation process is simple, and the reaction time is short.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step, iron chloride and enuatrol are scattered in the mixed liquor that contains n-hexane, deionized water and absolute ethyl alcohol, after heat treated, isolate supernatant liquor, will obtain iron oleate after this supernatant liquor oven dry with deionized water wash;
The molar ratio of described iron chloride and enuatrol is 1: 3
The volume ratio that contains n-hexane, deionized water and absolute ethyl alcohol in the described mixed liquor is: 4: 3: 7;
Described heat treated is meant: stirring reaction 4h under 70 ℃ of environment;
Second step, iron oleate and oleic acid are dispersed in the 1-octadecylene solution, protect and make the oil-soluble ferroferric oxide magnetic nanoparticle after adding thermal response; After reaction finished, product was cooled to room temperature, with absolute ethyl alcohol precipitation reaction product and after centrifugation precipitation is dispersed in the n-hexane, obtains oil-soluble ferroferric oxide magnetic nanoparticle dispersion liquid.
The mol ratio of described iron oleate and oleic acid is 1: 1;
Described protection adds thermal response and is meant at N
2Be warming up to reaction 30min under 320 ℃ of environment under the protective atmosphere;
The concentration of ferroferric oxide magnetic nanoparticle is 5-20mg/mL in the described oil-soluble ferroferric oxide magnetic nanoparticle dispersion liquid.
The 3rd step, in oil-soluble ferroferric oxide magnetic nanoparticle dispersion liquid, add non-polar solven and water successively, after ultrasonic emulsification is handled, obtain nanoemulsions;
Used non-polar solven is meant long alkane chain kind solvent, and as cyclohexane or n-hexane, its consumption is 0.5-10mL;
The consumption of described water is 1-10mL;
Described ultrasonic emulsification is handled and is meant the ultrasonic separating apparatus of use, and ultrasonic emulsification 1-10min uses power to be 80-300w;
The concentration of ferroferric oxide magnetic nanoparticle is 0.05-0.3mg/mL in the described nanoemulsions.
The 4th step, in nanoemulsions, add positive tetraethyl orthosilicate and the alkali lye and the stir process of heating, at last with the magnetic microsphere that obtains having coated with silica after absolute ethyl alcohol centrifugation and the drying.
The described stir process of heating was meant: at room temperature to 50 ℃ following stirring reaction 3-6 hour.
The volume ratio of described positive tetraethyl orthosilicate and nanoemulsions is 0.5-3%;
Described aqueous slkali is meant ammonia spirit or the 1mol/L sodium hydroxide solution of 25wt%, and the volume ratio of this aqueous slkali and nanoemulsions is 0.1-3%.
Operating process of the present invention is simple, and the magnetic microsphere of the coated with silica that makes has high magnetic content, and particle size distribution is homogeneous comparatively, can regulate the particle size of magnetic microsphere and the thickness of coated with silica layer by changing test parameters.The particle size of the magnetic microsphere after the coating is 50-400nm.In the particle size of control magnetic microsphere, just can simply control the magnetic content of microballoon.Surface coated silicon dioxide layer brings convenience then for further finishing and application.
Description of drawings
Fig. 1 is the transmission electron microscope picture of particle of the present invention.
Fig. 2 is the transmission electron microscope picture of particle of the present invention.
Fig. 3 is the transmission electron microscope picture of particle of the present invention.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
1. get 0.811g iron chloride and 4.5625g enuatrol, be dispersed in and contain the 35mL n-hexane, in the mixed solution of 15mL deionized water and 20mL absolute ethyl alcohol, at 70 ℃ of following stirring reaction 4h.With deionized water wash 3 times, separated and collected upper strata oil-soluble solution places oven for drying 24h, promptly obtains iron oleate, and is standby.
2. get 5mmol iron oleate and 3.24mL oleic acid, be dispersed in the 30mL 1-octadecylene solution, at N
2Be warming up to 320 ℃ under the protective atmosphere, reaction 30min.Promptly obtain the oil-soluble ferroferric oxide magnetic nanoparticle.After reaction finished, product was cooled to room temperature, with absolute ethyl alcohol precipitation reaction product, and repeatedly centrifugation, product is dispersed in the n-hexane at last, obtains oil-soluble magnetic-particle dispersion liquid.The concentration of ferroferric oxide magnetic nanoparticle is 15mg/mL.
3. the dispersion liquid of getting 25 μ L ferroferric oxide magnetic nanoparticles joins in the mixed solution of n-hexane/water, uses ultrasonic separating apparatus, and ultrasonic emulsification 5min uses power to be 180w, forms emulsion or microemulsion.Wherein, n-hexane 1mL, water 5mL.
4. in above-mentioned emulsion or microemulsion, add positive tetraethyl orthosilicate of 100 μ L and 100 μ L ammoniacal liquor, stirring reaction is 3 hours under the room temperature.For the product that obtains, with absolute ethyl alcohol centrifugation 3 times, and dry.The prepared magnetic microsphere average grain diameter that gets is 300nm.
Embodiment 2
1. get 0.811g iron chloride and 4.5625g enuatrol, be dispersed in and contain the 35mL n-hexane, in the mixed solution of 15mL deionized water and 20mL absolute ethyl alcohol, at 70 ℃ of following stirring reaction 4h.With deionized water wash 3 times, separated and collected upper strata oil-soluble solution places oven for drying 24h, promptly obtains iron oleate, and is standby.
2. get 5mmol iron oleate and 3.24mL oleic acid, be dispersed in the 30mL 1-octadecylene solution, under the N2 protective atmosphere, be warming up to 320 ℃, reaction 30min.Promptly obtain the oil-soluble ferroferric oxide magnetic nanoparticle.After reaction finished, product was cooled to room temperature, with absolute ethyl alcohol precipitation reaction product, and repeatedly centrifugation, product is dispersed in the n-hexane at last, obtains oil-soluble magnetic-particle dispersion liquid.The concentration of ferroferric oxide magnetic nanoparticle is 15mg/mL.
3. the dispersion liquid of getting 50 μ L ferroferric oxide magnetic nanoparticles joins in the mixed solution of n-hexane/water, uses ultrasonic separating apparatus, and ultrasonic emulsification 5min uses power to be 180w, forms emulsion or microemulsion.Wherein, n-hexane 1mL, water 5mL.
4. in above-mentioned emulsion or microemulsion, add positive tetraethyl orthosilicate of 100 μ L and 100 μ L ammoniacal liquor, stirring reaction is 3 hours under the room temperature.For the product that obtains, with absolute ethyl alcohol centrifugation 3 times, and dry.The prepared magnetic microsphere average grain diameter that gets is 100nm.
Embodiment 3
1. get 0.811g iron chloride and 4.5625g enuatrol, be dispersed in and contain the 35mL n-hexane, in the mixed solution of 15mL deionized water and 20mL absolute ethyl alcohol, at 70 ℃ of following stirring reaction 4h.With deionized water wash 3 times, separated and collected upper strata oil-soluble solution places oven for drying 24h, promptly obtains iron oleate, and is standby.
2. get 5mmol iron oleate and 3.24mL oleic acid, be dispersed in the 30mL 1-octadecylene solution, at N
2Be warming up to 320 ℃ under the protective atmosphere, reaction 30min.Promptly obtain the oil-soluble ferroferric oxide magnetic nanoparticle.After reaction finished, product was cooled to room temperature, with absolute ethyl alcohol precipitation reaction product, and repeatedly centrifugation, product is dispersed in the n-hexane at last, obtains oil-soluble magnetic-particle dispersion liquid.The concentration of ferroferric oxide magnetic nanoparticle is 15mg/mL.
3. the dispersion liquid of getting 100 μ L ferroferric oxide magnetic nanoparticles joins in the mixed solution of n-hexane/water, uses ultrasonic separating apparatus, and ultrasonic emulsification 5min uses power to be 180w, forms emulsion or microemulsion.Wherein, n-hexane 1mL, water 5mL.
4. in above-mentioned emulsion or microemulsion, add positive tetraethyl orthosilicate of 100 μ L and 100 μ L ammoniacal liquor, stirring reaction is 3 hours under the room temperature.For the product that obtains, with absolute ethyl alcohol centrifugation 3 times, and dry.The prepared magnetic microsphere average grain diameter that gets is 200nm.
Claims (8)
1. the preparation method with magnetic microsphere of coated with silica is characterized in that, may further comprise the steps:
The first step, iron chloride and enuatrol are scattered in the mixed liquor that contains n-hexane, deionized water and absolute ethyl alcohol, after heat treated, isolate supernatant liquor, will obtain iron oleate after this supernatant liquor oven dry with deionized water wash;
Second step, iron oleate and oleic acid are dispersed in the 1-octadecylene solution, protect and make the oil-soluble ferroferric oxide magnetic nanoparticle after adding thermal response; After reaction finished, product was cooled to room temperature, with absolute ethyl alcohol precipitation reaction product and after centrifugation precipitation is dispersed in the n-hexane, obtains oil-soluble ferroferric oxide magnetic nanoparticle dispersion liquid;
The 3rd step, in oil-soluble ferroferric oxide magnetic nanoparticle dispersion liquid, add non-polar solven and water successively, after ultrasonic emulsification is handled, obtain nanoemulsions;
The 4th step, in nanoemulsions, add positive tetraethyl orthosilicate and the alkali lye and the stir process of heating, at last with the magnetic microsphere that obtains having coated with silica after absolute ethyl alcohol centrifugation and the drying.
2. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, the molar ratio of described iron chloride and enuatrol is 1: 3.
3. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, the volume ratio that contains n-hexane, deionized water and absolute ethyl alcohol in the described mixed liquor is: 4: 3: 7.
4. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, the mol ratio of described iron oleate and oleic acid is 1: 1.
5. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, used non-polar solven is meant long alkane chain kind solvent, and its consumption is 0.5-10mL.
6. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, the consumption of used water is 1-10mL.
7. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, the volume ratio of described positive tetraethyl orthosilicate and nanoemulsions is 0.5-3%.
8. the preparation method with magnetic microsphere of coated with silica according to claim 1 is characterized in that, described aqueous slkali is meant the ammonia spirit of 25wt% or the sodium hydroxide solution of 1mol/L, and the volume ratio of this aqueous slkali and nanoemulsions is 0.1-3%.
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| CN101947472A (en) * | 2010-10-20 | 2011-01-19 | 新疆大学 | Coal liquefaction method and special catalyst thereof |
| CN102528027A (en) * | 2012-02-24 | 2012-07-04 | 哈尔滨工业大学 | Preparation method for gold-shell magnetic ellipsoid |
| CN103100358A (en) * | 2012-12-20 | 2013-05-15 | 华南理工大学 | Magnetic nanometer ion liquid composite particles as well as preparation method and application thereof |
| CN104013955A (en) * | 2014-06-18 | 2014-09-03 | 中国科学院过程工程研究所 | Oil-in-water emulsion free of surfactant and use thereof |
| CN104013979A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for targeting contrast agent for intestinal tracts |
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| CN105271433A (en) * | 2015-10-22 | 2016-01-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Hydrothermal synthesis preparation method of zinc doped superparamagnetic ferroferric oxide nano particle |
| CN106943970A (en) * | 2017-04-07 | 2017-07-14 | 安徽埃克利环境工程有限公司 | A kind of magnetic phase transition microcapsule based on ferroso-ferric oxide/silica compound wall materialses and preparation method thereof |
| CN107138093A (en) * | 2016-08-22 | 2017-09-08 | 浙江大学台州研究院 | The preparation method of magnetic force nanometer stirrer |
| CN107673361A (en) * | 2017-11-03 | 2018-02-09 | 吉林大学 | A kind of preparation method of the hollow silicon dioxide particle of more shells |
| CN108554325A (en) * | 2018-05-14 | 2018-09-21 | 苏州知益微球科技有限公司 | A kind of equal grain preparation of magnetic silicon dioxide microsphere |
| CN108641028A (en) * | 2018-05-14 | 2018-10-12 | 苏州知益微球科技有限公司 | A kind of preparation of magnetic silicon dioxide microsphere of size tunable |
| CN110853865A (en) * | 2019-11-20 | 2020-02-28 | 江南大学 | Preparation method and application of ferroferric oxide single-layer nano film |
| CN112023841A (en) * | 2020-07-24 | 2020-12-04 | 无锡迈科为生物科技有限公司 | Preparation method of uniform magnetic microspheres for extracting high-load nucleic acid |
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2009
- 2009-12-25 CN CN 200910200743 patent/CN101783217A/en active Pending
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| CN101947472A (en) * | 2010-10-20 | 2011-01-19 | 新疆大学 | Coal liquefaction method and special catalyst thereof |
| CN101947472B (en) * | 2010-10-20 | 2013-05-22 | 新疆大学 | Coal liquefaction method and special catalyst thereof |
| CN102528027A (en) * | 2012-02-24 | 2012-07-04 | 哈尔滨工业大学 | Preparation method for gold-shell magnetic ellipsoid |
| CN102528027B (en) * | 2012-02-24 | 2013-06-26 | 哈尔滨工业大学 | Preparation method for gold-shell magnetic ellipsoid |
| CN103100358A (en) * | 2012-12-20 | 2013-05-15 | 华南理工大学 | Magnetic nanometer ion liquid composite particles as well as preparation method and application thereof |
| CN103100358B (en) * | 2012-12-20 | 2014-12-31 | 华南理工大学 | Magnetic nanometer ion liquid composite particles as well as preparation method and application thereof |
| CN104013979A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for targeting contrast agent for intestinal tracts |
| CN104013955A (en) * | 2014-06-18 | 2014-09-03 | 中国科学院过程工程研究所 | Oil-in-water emulsion free of surfactant and use thereof |
| CN104013955B (en) * | 2014-06-18 | 2016-02-24 | 中国科学院过程工程研究所 | A kind of not containing O/w emulsion and uses thereof of surfactant |
| CN104312217A (en) * | 2014-07-25 | 2015-01-28 | 合肥旭阳铝颜料有限公司 | A magnetic Fe3O4 nano-particle/flake aluminium pigment composite nanometer material |
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| CN105271433A (en) * | 2015-10-22 | 2016-01-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Hydrothermal synthesis preparation method of zinc doped superparamagnetic ferroferric oxide nano particle |
| CN107138093B (en) * | 2016-08-22 | 2020-04-21 | 浙江大学台州研究院 | Preparation method of magnetic nano stirrer |
| CN107138093A (en) * | 2016-08-22 | 2017-09-08 | 浙江大学台州研究院 | The preparation method of magnetic force nanometer stirrer |
| CN106943970A (en) * | 2017-04-07 | 2017-07-14 | 安徽埃克利环境工程有限公司 | A kind of magnetic phase transition microcapsule based on ferroso-ferric oxide/silica compound wall materialses and preparation method thereof |
| CN107673361A (en) * | 2017-11-03 | 2018-02-09 | 吉林大学 | A kind of preparation method of the hollow silicon dioxide particle of more shells |
| CN108554325A (en) * | 2018-05-14 | 2018-09-21 | 苏州知益微球科技有限公司 | A kind of equal grain preparation of magnetic silicon dioxide microsphere |
| CN108641028A (en) * | 2018-05-14 | 2018-10-12 | 苏州知益微球科技有限公司 | A kind of preparation of magnetic silicon dioxide microsphere of size tunable |
| CN110853865A (en) * | 2019-11-20 | 2020-02-28 | 江南大学 | Preparation method and application of ferroferric oxide single-layer nano film |
| CN112023841A (en) * | 2020-07-24 | 2020-12-04 | 无锡迈科为生物科技有限公司 | Preparation method of uniform magnetic microspheres for extracting high-load nucleic acid |
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Application publication date: 20100721 |