CN103638880B - A kind of preparation method of porous magnetic microballoon - Google Patents

A kind of preparation method of porous magnetic microballoon Download PDF

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CN103638880B
CN103638880B CN201310712657.6A CN201310712657A CN103638880B CN 103638880 B CN103638880 B CN 103638880B CN 201310712657 A CN201310712657 A CN 201310712657A CN 103638880 B CN103638880 B CN 103638880B
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fecl
porous magnetic
preparation
magnetic microballoon
microballoon
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CN103638880A (en
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马烽
尤龙
董玉欢
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Qilu University of Technology
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Abstract

The present invention relates to a kind of preparation method of porous magnetic microballoon, step is as follows: (1) is by FeCl 3g6H 2o and FeCl 2g4H 2o is dissolved in surfactant solution, stirring and dissolving; (2) alkaline matter is added to pH8 ~ 14; (3) ageing 6 ~ 48h at 20 ~ 90 DEG C; Or, at 30 ~ 300 DEG C of Hydrothermal Synthesis 6 ~ 48h, collect solid product; (4) solid product is placed in washing agent to stir or supersound washing, vacuum drying, obtains porous magnetic microballoon.Porous magnetic microballoon of the present invention, specific area is high, and the material amount of loading with is high, and channel diameter distribution is homogeneous, and aperture can modulation, and microballoon hole wall is thick and hydrothermal stability is very high, has wide practical use in fields such as catalysis, separation, biological medicine and nano materials.

Description

A kind of preparation method of porous magnetic microballoon
Technical field
The present invention relates to a kind of preparation method of porous magnetic microballoon, belong to technical field prepared by magnetic microsphere.
Background technology
Magnetic microsphere is widely applied to the numerous areas such as biomedicine, cytology and separation engineering as a kind of novel magnetic materials.At biomedical sector, magnetic microsphere can, as pharmaceutical carrier, enter in patient body, under additional magnetic fields, shifts to diseased region, release medicine, and then plays the object for the treatment of.Can drug effect be improved with magnetic microsphere as pharmaceutical carrier, reduce the injury of agents on normal cells.At environmental area, magnetic microsphere can the harmful ion such as Adsorption of Heavy Metals, thus extensively should be made decontamination material.But existing magnetic microsphere mostly is medicine ball, specific area is little causes that drugloading rate is few or adsorbance is few.The preparation method of magnetic microsphere has the conditions such as pyroreaction more, very easily causes the structural deterioration of magnetic microsphere.
Chinese patent literature CN102417208A(application number: 201110225433.3) disclose mesoporous magnetic ferroferric oxide, preparation method and application; Its nano particle size is 10-50nm, and aperture is at 6-10nm, and surface area is 21-90m 2/ g; Prepare according to following step: take FeCl 36H 2o and ethylene glycol, stir the yellow solution forming clarification, then add NaAc, in second diene triamine or reacting ethylenediamine still, 90-180 DEG C of reaction 4-10h, naturally cools to room temperature, centrifugation, washes 4 times with water, dry black solid particle, productive rate 84%, particle diameter 10-40nm.Can be used as the carrier of anti-tumor drugs targeting, mesoporous magnetic ferroferric oxide has the controlled advantage of dispersiveness, good stability, size, is beneficial to suitability for industrialized production.
Chinese patent literature CN101417822A(application number: the preparation method 200810051456.5) disclosing super paramagnetic mesoporous ferriferrous oxide nano particle, it is the preparation method of superparamagnetic nano particle of single dispersing, hydrophilic and applicable biologic applications.Adopt general chemistry reagent to be raw material, be coating agent with ethylenediamine, avoid the surfactant using other.Monodispersed superparamagnetic nano particle effectively can be prepared on a large scale by the ratio controlling ethylenediamine and ferric trichloride, overcome the shortcoming reagent that such as particle size heterogeneity, high temperature and use are valuable of existing synthesis ferriferrous oxide nano-particle, for biological medical field and bio-separation provide the foundation material.The mesoporous superparamagnetic nano particle obtained by transport at medicine and the target of gene with treat, the field such as to be separated of Magnetic resonance imaging, magnetic heat cure and protein has important purposes.
Although magnetic ion has loose structure disclosed in above-mentioned patent document, the space, hole of magnetic ion is little, and specific area is little, cause apply biomedicine field time drugloading rate few.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of porous magnetic microballoon.
Technical scheme of the present invention is as follows:
A preparation method for porous magnetic microballoon, step is as follows:
(1) by FeCl 36H 2o:FeCl 24H 2o is 3:(1.5 ~ 6 in molar ratio) be dissolved in surfactant solution, 30 ~ 70 DEG C of stirring and dissolving 20 ~ 40min, described FeCl 36H 2o and FeCl 24H 2the gross mass of O and the volume ratio of surfactant solution are 0.01 ~ 0.1g/ml; Described surfactant is softex kw or hexadecyltrimethylammonium chloride;
(2) alkaline matter is added to pH8 ~ 14;
(3) ageing 6 ~ 48h at 20 ~ 90 DEG C; Or, at 30 ~ 300 DEG C of Hydrothermal Synthesis 6 ~ 48h, collect solid product;
(4) solid product is placed in washing agent at 25 ~ 80 DEG C of agitator treating 4 ~ 12h, or, solid product is placed in washing agent supersound washing 4 ~ 12h; 25 ~ 100 DEG C of vacuum drying 4 ~ 12h, obtain porous magnetic microballoon.
According to the present invention, preferably, the FeCl described in step (1) 36H 2o:FeCl 24H 2the mol ratio of O is 3:(1.5 ~ 3), the mass concentration of described surfactant solution is 0.002 ~ 0.2g/ml; Described FeCl 36H 2o and FeCl 24H 2the gross mass of O and the volume ratio 0.03 ~ 0.06g/ml of surfactant solution.
According to the present invention, preferably, by FeCl in described step (1) 36H 2o and FeCl 24H 2o stirring and dissolving adds expanding agent again after surface activating solution, and stirring and dissolving is even, and described expanding agent and the mass volume ratio of surface activating solution are 0.01 ~ 0.2g/ml, and described expanding agent is tetramethyl benzidine or mesitylene.
According to the present invention, preferably, the alkaline matter described in step (2) is selected from one or more mixing in NaOH, potassium hydroxide, ammoniacal liquor, sodium alkoxide, potassium alcoholate.
According to the present invention, preferably, the Aging Temperature described in step (3) is 45 ~ 75 DEG C, and described Hydrothermal Synthesis temperature is 100 ~ 200 DEG C.
According to the present invention, preferably, the washing agent described in step (4) is ethanol or isopropyl alcohol, and the frequency of described supersound washing is 4000 ~ 40000Hz.
The washing process of step of the present invention (4) is surfactant and expanding agent fully to dissolve removal.In the preparation process of porous magnetic microballoon, formation framework assembled by surfactant, and magnetic particle is assembled in the space of framework, forms magnetic porous microspheres after removing surfactant.
Porous magnetic microballoon prepared by the present invention is the chondritic that many skies run through, aperture 5 ~ 40nm, microballoon average diameter 50 ~ 200nm, specific area 40 ~ 130m 2/ g, saturation magnetization 70 ~ 110emu/g.
The invention has the beneficial effects as follows:
1, surfactant of the present invention is thread crosslinked together, and the space stayed after removing makes each hole run through microballoon, and form porous magnetic microballoon, specific area is high, and the material amount of loading with is high.
2, the present invention selects FeCl 36H 2o and FeCl 24H 2o is as source of iron, and raw material is easy to get, with low cost; Surfactant used is soluble in ethanol or aqueous isopropanol, simple in the removal process of surfactant.
3, the channel diameter distribution of the porous magnetic microballoon prepared of the present invention is homogeneous, and aperture can modulation, and microballoon hole wall is thick and hydrothermal stability is very high, has wide practical use in fields such as catalysis, separation, biological medicine and nano materials.
4, preparation method of the present invention is simple, and do not need the processing steps such as high-temperature calcination, energy consumption is low.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of porous magnetic microballoon prepared by the embodiment of the present invention 1.
Fig. 2 is the hysteresis curve of porous magnetic microballoon prepared by the embodiment of the present invention 1.
Detailed description of the invention
Below by specific embodiment, the present invention will be further described, but be not limited thereto.
Raw materials usedly in embodiment be conventional reagent, commercial products, device therefor is conventional equipment.
Embodiment 1
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 2g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:1.5) to be dissolved in 50ml concentration be in the softex kw solution of 0.04g/ml, 50 DEG C of stirring and dissolving 20min;
(2) NaOH is added to pH11 ~ 12;
(3) proceed in autoclave, 140 DEG C of Hydrothermal Synthesis 36h, collect solid product;
(4) solid product is placed in supersound washing 6h under ethanol 20000Hz frequency, 40 DEG C of vacuum drying 6h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 22nm, and microballoon average diameter is 190nm, and specific area is 89.23m 2/ g, saturation magnetization is 82.11emu/g.
Fig. 1 is transmission electron microscope (TEM) photo of porous magnetic microballoon prepared by the present embodiment, and as shown in Figure 1, porous magnetic microballoon grey black is alternate, and grey parts is the hole running through microballoon.
Fig. 2 is the hysteresis curve of porous magnetic microballoon prepared by the present embodiment, and as shown in Figure 2, porous magnetic microballoon has magnetic, and the intensity of magnetization is high.
Embodiment 2
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 2g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:2) to be dissolved in 50ml concentration be in the softex kw solution of 0.04g/ml, 50 DEG C of stirring and dissolving 20min, add 1.5g mesitylene afterwards and continue stirring and dissolving 20min;
(2) NaOH is added to pH11 ~ 12;
(3) proceed in autoclave, 140 DEG C of Hydrothermal Synthesis 24h, collect solid product;
(4) solid product is placed in supersound washing 6h under ethanol 20000Hz frequency, 40 DEG C of vacuum drying 6h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 32nm, and microballoon average diameter is 100nm, and specific area is 53.45m 2/ g, saturation magnetization is 79.62emu/g.
Embodiment 3
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 2g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:5) to be dissolved in 50ml concentration be in the softex kw solution of 0.1g/ml, 30 DEG C of stirring and dissolving 20min;
(2) NaOH is added to pH11 ~ 12;
(3) proceed in autoclave, 140 DEG C of Hydrothermal Synthesis 24h, collect solid product;
(4) solid product is placed in supersound washing 4h under ethanol 10000Hz frequency, 25 DEG C of vacuum drying 4h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 14nm, and microballoon average diameter is 50nm, and specific area is 98.93m 2/ g, saturation magnetization is 85.40emu/g.
Embodiment 4
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 2g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:2) to be dissolved in 50ml concentration be in the softex kw solution of 0.02g/ml, 30 DEG C of stirring and dissolving 20min;
(2) NaOH is added to pH11 ~ 12;
(3) proceed in autoclave, 140 DEG C of Hydrothermal Synthesis 24h, collect solid product;
(4) solid product is placed in supersound washing 4h under ethanol 40000Hz frequency, 25 DEG C of vacuum drying 4h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 10nm, and microballoon average diameter is 50nm, and specific area is 107.56m 2/ g, saturation magnetization is 103.47emu/g.
Embodiment 5
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 1.5g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:3) to be dissolved in 50ml concentration be in the softex kw solution of 0.01g/ml, 45 DEG C of stirring and dissolving 40min;
(2) potassium hydroxide is added to pH10 ~ 11;
(3) proceed in autoclave, 300 DEG C of Hydrothermal Synthesis 48h, collect solid product;
(4) solid product is placed in supersound washing 4h under ethanol 30000Hz frequency, 25 DEG C of vacuum drying 4h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 20nm, and microballoon average diameter is 160nm, and specific area is 84.03m 2/ g, saturation magnetization is 72.17emu/g.
Embodiment 6
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 3g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:4) to be dissolved in 50ml concentration be in the softex kw solution of 0.03g/ml, 40 DEG C of stirring and dissolving 30min;
(2) NaOH is added to pH11 ~ 12;
(3) proceed in autoclave, 100 DEG C of Hydrothermal Synthesis 40h, collect solid product;
(4) solid product is placed in supersound washing 10h under isopropyl alcohol 20000 frequency, 30 DEG C of vacuum drying 10h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 20nm, and microballoon average diameter is 130nm, and specific area is 93.20m 2/ g, saturation magnetization is 96.77emu/g.
Embodiment 7
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 2g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:5) to be dissolved in 50ml concentration be in the softex kw solution of 0.04g/ml, 35 DEG C of stirring and dissolving 30min; Add 0.5g tetramethyl benzidine again, stirring and dissolving is even;
(2) NaOH is added to pH12 ~ 13;
(3) ageing 48h at 20 DEG C, collects solid product;
(4) solid product is placed in ethanol 25 DEG C of agitator treating 10h, 30 DEG C of vacuum drying 10h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 10nm, and microballoon average diameter is 98nm, and specific area is 118.81m 2/ g, saturation magnetization is 93.64emu/g.
Embodiment 8
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 3g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:6) to be dissolved in 50ml concentration be in the hexadecyltrimethylammonium chloride solution of 0.05g/ml, 40 DEG C of stirring and dissolving 30min;
(2) NaOH is added to pH11 ~ 12;
(3) ageing 6h at 90 DEG C, collects solid product;
(4) solid product is placed in ethanol 80 DEG C of agitator treating 4h, 100 DEG C of vacuum drying 4h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 21nm, and microballoon average diameter is 60nm, and specific area is 61.32m 2/ g, saturation magnetization is 94.46emu/g.
Embodiment 9
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 1g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:4) to be dissolved in 50ml concentration be in the softex kw solution of 0.02g/ml, 40 DEG C of stirring and dissolving 30min; Add 2g mesitylene again, continue stirring and dissolving 20min;
(2) NaOH is added to pH13 ~ 14;
(3) ageing 8h at 70 DEG C, collects solid product;
(4) solid product is placed in ethanol 40 DEG C of agitator treating 8h, 60 DEG C of vacuum drying 8h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 27nm, and microballoon average diameter is 90nm, and specific area is 52.18m 2/ g, saturation magnetization is 106.69emu/g.
Embodiment 10
A preparation method for porous magnetic microballoon, step is as follows:
(1) be the FeCl of 3.5g by gross mass 36H 2o and FeCl 24H 2o mixture (FeCl 36H 2o:FeCl 24H 2o mol ratio is 3:3) to be dissolved in 50ml concentration be in the softex kw solution of 0.01g/ml, 35 DEG C of stirring and dissolving 30min;
(2) potassium hydroxide is added to pH11 ~ 12;
(3) ageing 6h at 40 DEG C, collects solid product;
(4) solid product is placed in supersound washing 10h under ethanol 16000Hz frequency, 50 DEG C of vacuum drying 8h, obtain porous magnetic microballoon.
Porous magnetic microballoon prepared by the present embodiment, aperture is 20nm, and microballoon average diameter is 55nm, and specific area is 78.38m 2/ g, saturation magnetization is 79.30emu/g.
Experimental example
The material load performance of porous magnetic prepared by this experimental example research performation example 1-10:
Using methotrexate (MTX) as the medicine amount of loading with Experimental agents, adopt the drugloading rate of UV absorptiometry to porous magnetic microballoon to measure, result is as shown in table 1
Table 1 porous magnetic micro-ball load results of property
As shown in Table 1, how empty magnetic microsphere load capacity prepared by the present invention be high, has wide practical use in fields such as catalysis, separation, biological medicine and nano materials.

Claims (1)

1. a preparation method for porous magnetic microballoon, step is as follows:
(1) by FeCl 36H 2o:FeCl 24H 2o is 3:(1.5 ~ 6 in molar ratio) be dissolved in surfactant solution, 30 ~ 70 DEG C of stirring and dissolving 20 ~ 40min, described FeCl 36H 2o and FeCl 24H 2the gross mass of O and the volume ratio of surfactant solution are 0.01 ~ 0.1g/mL; Described surfactant is softex kw or hexadecyltrimethylammonium chloride;
By FeCl 36H 2o and FeCl 24H 2o stirring and dissolving adds expanding agent again after surfactant solution, and stirring and dissolving is even, and described expanding agent and the mass volume ratio of surfactant solution are 0.01 ~ 0.2g/mL, and described expanding agent is tetramethyl benzidine or mesitylene;
(2) alkaline matter is added to pH 8 ~ 14;
(3) ageing 6 ~ 48h at 20 ~ 90 DEG C; Or, at 30 ~ 300 DEG C of Hydrothermal Synthesis 6 ~ 48h, collect solid product;
(4) solid product is placed in washing agent at 25 ~ 80 DEG C of agitator treating 4 ~ 12h, or, solid product is placed in washing agent supersound washing 4 ~ 12h; 25 ~ 100 DEG C of vacuum drying 4 ~ 12h, obtain porous magnetic microballoon.
2 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the FeCl described in step (1) 36H 2o:FeCl 24H 2the mol ratio of O is 3:(1.5 ~ 3).
3 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the mass concentration of the surfactant solution described in step (1) is 0.002 ~ 0.2g/mL.
4 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the FeCl described in step (1) 36H 2o and FeCl 24H 2the gross mass of O and the volume ratio 0.03 ~ 0.06g/mL of surfactant solution.
5 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the alkaline matter described in step (2) is selected from one or more mixing in NaOH, potassium hydroxide, ammoniacal liquor, sodium alkoxide, potassium alcoholate.
6 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the Aging Temperature described in step (3) is 45 ~ 75 DEG C, and described Hydrothermal Synthesis temperature is 100 ~ 200 DEG C.
7 .the preparation method of porous magnetic microballoon according to claim 1, is characterized in that, the washing agent described in step (4) is ethanol or isopropyl alcohol, and the frequency of described supersound washing is 4000 ~ 40000 Hz.
CN201310712657.6A 2013-12-20 2013-12-20 A kind of preparation method of porous magnetic microballoon Expired - Fee Related CN103638880B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2415427A (en) * 2004-06-23 2005-12-28 Reagent Mine Ltd A process for the manufacture of magnetic particles
CN101830516A (en) * 2010-05-18 2010-09-15 浙江大学 Method for preparing nano ferroferric oxide particles
CN102502877A (en) * 2011-10-18 2012-06-20 南开大学 Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres
CN103268797A (en) * 2013-05-07 2013-08-28 福州大学 Hydrophilic magnetic mesoporous microsphere and production method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2415427A (en) * 2004-06-23 2005-12-28 Reagent Mine Ltd A process for the manufacture of magnetic particles
CN101830516A (en) * 2010-05-18 2010-09-15 浙江大学 Method for preparing nano ferroferric oxide particles
CN102502877A (en) * 2011-10-18 2012-06-20 南开大学 Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres
CN103268797A (en) * 2013-05-07 2013-08-28 福州大学 Hydrophilic magnetic mesoporous microsphere and production method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
磁响应纳米四氧化三铁/壳聚糖复合微球的制备及特性;李凤生等;《磁性材料及器件》;20021230;第33卷(第06期);第2页第2.2节第1段 *

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