CN100405511C - Water-base magnetic liquid and producing method thereof - Google Patents
Water-base magnetic liquid and producing method thereof Download PDFInfo
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- CN100405511C CN100405511C CNB2005101002306A CN200510100230A CN100405511C CN 100405511 C CN100405511 C CN 100405511C CN B2005101002306 A CNB2005101002306 A CN B2005101002306A CN 200510100230 A CN200510100230 A CN 200510100230A CN 100405511 C CN100405511 C CN 100405511C
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Abstract
The present invention relates to water-base magnetic liquid and a preparation method thereof. The aim of the present invention is to overcome the defects existing in the prior art and provide water-base magnetic liquid with good biocompatibility and small particle hydrodynamics diameters and a preparation method of the water-base magnetic liquid. The present invention uses carboxyl polysaccharide as the stabilizer of the magnetic liquid; the method of chemical coprecipitation is used for preparing ferroferric oxide water base magnetic liquid under the existence of the stabilizer, or the method of chemical coprecipitation is used for preparing nanometer ferroferric oxide particles firstly, and then surface modification is carried out to prepare the magnetic iron oxide water base magnetic liquid. Most of the carboxyl polysaccharide has the characteristics of no poison and good biocompatibility, side chains of molecular chains contains abundant active group carboxyl and are easily connected with medicine, cells, protein or genes, so the present invention is suitable for the field of biological medicine such as carriers of magnetic targeted drugs, thermotherapy in magnetic liquid cells, nuclear magnetic resonance contrast imaging agents, magnetic separation, etc.
Description
Technical field
The present invention relates to a kind of water-base magnetic liquid and preparation method thereof.
Technical background
So-called magnetic liquid is meant the nano magnetic particle high degree of dispersion and the stable colloidal dispersion that forms in carrier fluid that are adsorbed with stabilizer.Mainly form by nano magnetic particle, stabilizer and carrier fluid.Water-base magnetic liquid mainly can be divided three classes according to its used stabilizer types difference: 1, adopt water miscible organic molecule such as amino acid, citric acid, folic acid etc. to be chela and agent and stabilizer at present; 2, utilize surfactant to form double-deck absorption mode on the nano magnetic particle surface and prepare water-base magnetic liquid, used surfactant comprises aliphatic acid, N-acylamino acid etc.; 3, adopting the macromolecule with hydrophilic radical is stabilizer, and used stabilizer mainly contains polysaccharide, protein-based, polyacrylic, polyacrylamide etc.Currently used polysaccharide stabilizer mostly is glucan, shitosan, starch etc. greatly, owing to only have hydroxyl on these polysaccharide molecule chains, active force between they and the nano ferriferrous oxide granule is little, modified effect is undesirable, surface potential is low, granule stability is relatively poor, and the chemical active radical of particle surface is less after the modification, with medicine, cell, protein or gene to be connected technology comparatively complicated.Shortcomings such as particularly currently used preparation method makes this class water-base magnetic liquid exist particle hydrodynamics diameter too big, generally surpasses 300nm, and external coating is thick, and saturation magnetization is low, and perhaps biocompatibility is relatively poor.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, a kind of good biocompatibility, water-base magnetic liquid that particle hydrodynamics diameter is little and preparation method thereof are provided.
The invention provides a kind of water-base magnetic liquid, mainly by nano ferriferrous oxide granule, stabilizer and water are formed, be characterized in adopting carboxylated polysaccharide as the magnetic liquid stabilizer, most carboxylated polysaccharides have nontoxic, the characteristics of good biocompatibility, the strand side chain contains abundant active group carboxyl, can form chemical bond with the nano ferriferrous oxide granule surface combines, and the nano ferriferrous oxide granule of carboxylated polysaccharide modification is easy and medicine, cell, protein or gene connect, and are applicable to the magnetic target medicine carrier, thermotherapy in the magnetic liquid cell, nulcear magnetic resonance (NMR) contrast developer, biomedical sectors such as magnetic separation.The carboxylated polysaccharide that is adopted is a kind of in the alkali metal salt of alginic acid or alginic acid, also can be in the alkali metal salt of Sensor Chip CM 5, Sensor Chip CM 5 a kind of.The weight average molecular weight of general carboxylated polysaccharide is preferably between 10,000～20,000 between 10,000～50,000.If the weight average molecular weight of carboxylated polysaccharide is too little, carboxylated polysaccharide is less in the adsorbance on nano ferriferrous oxide granule surface, and the steric hindrance that forms is less, is unfavorable for the stable of nano particle; If the weight average molecular weight of carboxylated polysaccharide is too big, then the viscosity of reaction system can be very big, and flock together easily between the modified particles, and granule stability is also relatively poor.
The present invention adopts chemical coprecipitation to prepare the tri-iron tetroxide water-base magnetic liquid in the presence of stabilizer, or adopt elder generation to prepare nano ferriferrous oxide granule with chemical coprecipitation, carry out the method that surface modification prepares the tri-iron tetroxide water-base magnetic liquid then, the chemical equation that chemical coprecipitation prepares magnetic particles of ferroferric oxide is:
FeSO
4·7H
2O+2FeCl
3·6H
2O+8NH
4OH＝Fe
3O
4+NH
4Cl+(NH
4)
2SO
4+23H
2O
Or FeCl
24H
2O+2FeCl
36H
2O+8NH
4OH=Fe
3O
4+ 8NH
4Cl+20H
2O
For preparing carboxylated polysaccharide improved ferroferric oxide water-base magnetic liquid of the present invention, can take the technology of the following stated:
1. there is synthesis of nano ferriferrous oxide particles down in carboxylated polysaccharide
It is 30%～65% the aqueous solution that ferric trichloride is made into mass concentration, it is 15%～30% the aqueous solution that ferrous chloride or ferrous sulfate are mixed with mass concentration, by ferrous chloride or ferrous sulfate: both mol ratios of ferric trichloride are 1.0～1.4: 2 proportionings, two kinds of solution mixing are made into the molysite mixed solution, carboxylated polysaccharide is dissolved in the concentrated ammonia liquor of 25Wt%～30Wt% and is made into carboxylated polysaccharide ammoniacal liquor mixed solution, by ammoniacal liquor: the mol ratio of ferric trichloride is 12～40: 1, carboxylated polysaccharide is 2～5: 1 ratio to the mass ratio of tri-iron tetroxide, molysite mixed solution and carboxylated polysaccharide ammoniacal liquor mixed solution are under agitation mixed, under agitation reacted then 20～60 minutes, mixing speed is controlled at 300～1800 rev/mins, reaction temperature is controlled between 50～99 ℃, obtains containing unstable oarse-grained water base Fe 3 O 4 magnetic liquid;
2. unsettled bulky grain is removed in centrifugation
With centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, the bulky grain of removal precipitation, the even also stable dispersion of assurance nano ferriferrous oxide granule size is collected supernatant liquor as stable water-base magnetic liquid in water.
The 1. described ammonia volume of step is an ammoniacal liquor: both mol ratios of ferric trichloride should be controlled at 12～40: 1, and the pH value stabilization that could guarantee reaction system like this and only could form stable tri-iron tetroxide nucleus under this pH condition between 8～9.5.Described reaction temperature should be stabilized between 50～99 ℃, if reaction temperature is lower than 50 ℃, tri-iron tetroxide crystal grain is difficult for growing up, and magnetic is very weak; The reaction temperature of this reaction system is high more to help growing up of crystal grain more, if reaction temperature is controlled between 90～99 ℃, then the average crystal grain particle diameter of tri-iron tetroxide can reach 8nm, and the magnetic that can reach is stronger.
In order further to remove carboxylated polysaccharide remaining in the water-base magnetic liquid, can adopt the method for cyclic washing ultrafiltration to carry out, the method that also can adopt gel chromatography to filter is carried out, and is last, adopts the method for ultrafiltration or decompression distillation that water-base magnetic liquid is concentrated into required concentration.
To achieve the object of the present invention, also can adopt chemical coprecipitation to prepare nano ferriferrous oxide granule earlier, carry out surface modification then and prepare water-base magnetic liquid, may further comprise the steps:
1. nano ferriferrous oxide granule is synthetic
It is 2%～65% the aqueous solution that ferric trichloride is made into mass concentration, it is 1%～30% the aqueous solution that ferrous chloride or ferrous sulfate are mixed with mass concentration, by ferrous chloride or ferrous sulfate: both mol ratios of ferric trichloride are that 1.0～1.4: 2 proportionings are mixed two kinds of solution and are made into the molysite mixed solution, by ferrous chloride or ferrous sulfate: ferric trichloride: ammoniacal liquor three's mol ratio is 1.0～1.4: 2: 8～16 proportionate relationship, the concentrated ammonia liquor that under agitation adds molysite mixed solution and 25Wt%～30Wt% simultaneously, mixing speed is controlled at 400～2000 rev/mins, reaction temperature is stabilized between 30～60 ℃, reacted 10～30 minutes, and obtained the nanometer Fe 3 O 4 magnetic particle;
2. the washing of nano ferriferrous oxide granule and ultrasonic dispersion
With the distilled water nanometer Fe 3 O 4 magnetic particle that obtains of cleaning reaction repeatedly, making concentration is that the conductivity of the ferroferric oxide gel solution of 0.3～1g/100ml is reduced to less than 100 μ s/cm ultrasonic then dispersion 1～5 minute;
3. nano ferriferrous oxide granule surface modification and the dispersion in water
Concentration be in the ferroferric oxide gel solution of 0.3～1g/100ml by tri-iron tetroxide: both mass ratioes of carboxylated polysaccharide are 1: 0.25～2 to add carboxylated polysaccharides, regulate between this system pH to 3～6, continuous stirring 30～60 minutes is reflected in 50～80 ℃ of water-baths and carries out; After question response finishes, wash with water repeatedly, make that to contain tri-iron tetroxide concentration be that the conductivity of the reaction system of 0.4～4g/100ml is reduced to less than 100 μ s/cm, the pH value is between 6.5～7.5, ultrasonic then dispersion 1～5 minute makes water base Fe 3 O 4 magnetic liquid.
Above-mentioned steps is the washing and the ultrasonic dispersion of middle nano ferriferrous oxide granule 2., should make and wash back concentration the conductivity that is the ferroferric oxide gel solution of 0.3～1g/100ml to be reduced to less than 100 μ s/cm, this be because if the conductivity of solution greater than 100 μ s/cm, illustrate and contain more electrolyte in the solution, the stable dispersion that is unfavorable for the nano ferriferrous oxide colloidal solid, therefore, the conductivity of the ferroferric oxide gel solution after the washing is reduced to less than 30 μ s/cm.
3. middle nano ferriferrous oxide granule surface modification of step and the dispersion in water, tri-iron tetroxide: both mass ratioes of carboxylated polysaccharide should be controlled at 1: 0.25～2, if the consumption of carboxylated polysaccharide is too low, then carboxylated polysaccharide with very few, is unfavorable for the stable and dispersion of particle in the adsorbance on nano ferriferrous oxide granule surface; If the consumption of carboxylated polysaccharide is too high, the existence of unnecessary carboxylated polysaccharide is unfavorable for the stable and waste raw material of particle after the modification.Said modification pH value should be controlled between 3～6, if the pH value is too low, the dissolubility of carboxylated polysaccharide is relatively poor, is unfavorable for the adsorption of modification of carboxylated polysaccharide on the ferriferrous oxide particles surface; If the pH value is too high, then can increase because of the electronegativity on nano ferriferrous oxide granule surface, be unfavorable for the absorption of electronegative carboxylated polysaccharide.
Step is last in 3. to adopt ultrasonic dispersion, can further help the nano ferriferrous oxide granule of surface modification to be dispersed in the water.
The present invention has following beneficial effect compared with the prior art:
1. the prepared water-base magnetic liquid of the present invention is stabilizer with the carboxylated polysaccharide, good biocompatibility;
2. side chain carboxyl group is compared with the pendant hydroxyl group of polysaccharide, can be anchored on the nano ferriferrous oxide nano grain surface well, and easilier is connected with medicine, cell, protein or gene;
3. in addition, the existence of surperficial carboxyl makes particle after the modification at pH value 5.5～9.5 scope inner surface belt negative electricity, and the average surface current potential is-20～-50mV, can in pH value 5～10 scopes, keep stable;
4. gained nano particle magnetic nuclear average grain diameter is 7～12nm after the modification, average hydrodynamics diameter is 30～60nm, the iron-holder of magnetic liquid is 10～40mg/ml, saturation magnetization can reach 1～10kA/m, is applicable to biomedical sectors such as thermotherapy in magnetic target medicine carrier, the magnetic liquid cell, nulcear magnetic resonance (NMR) contrast developer, magnetic separation.
The assay method of above data is: the saturation magnetization of water-base magnetic liquid adopts vibrating specimen magnetometer to measure, the diameter of magnetic nuclear adopts transmission electron microscope and X-ray diffraction to measure, the hydrodynamics diameter adopts photon correlation spectroscopy to measure, surface potential detection carries out on Ma Erwen 3000HSA Zetasizer instrument, and iron-holder adopts the Phen method to measure.
Description of drawings
Fig. 1 is the nuclear shell structure schematic diagram of carboxylated polysaccharide modified Nano magnetic ferroferric oxide particle in the water-base magnetic liquid of the present invention;
The transmission electron microscope photo of the water-base magnetic liquid that Fig. 2 makes for the inventive method;
The transmission electron microscope photo of the medicament-carried nano particle of the water-base magnetic liquid that Fig. 3 makes for the inventive method.
Embodiment
The present invention is described further below in conjunction with accompanying drawing.
Embodiment 1
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 5g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into molysite mixed solution, ferrous sulfate with two kinds of solution mixing: both mol ratios of ferric trichloride=1: 2.With the 20g weight average molecular weight is that 20,000 Na-alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution, at this moment ammoniacal liquor in the concentrated ammonia liquor that 100ml concentration is 25Wt%: the mol ratio of ferric trichloride is 40: 1, and carboxylated polysaccharide is 5: 1 to the mass ratio of tri-iron tetroxide.Molysite mixed solution and sodium alginate ammoniacal liquor mixed solution are mixed under 800 rev/mins stirring, stir reaction down 40 minutes then, reaction temperature is stabilized in 90 ℃; After reaction finishes, with centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, remove the bulky grain of precipitation, guarantee that the even also stable dispersion of nano ferriferrous oxide granule size is in water, collect supernatant liquor as stable water base Fe 3 O 4 magnetic liquid, the magnetic liquid that can to obtain about 30ml iron-holder be 9mg/ml, saturation magnetization is about 1.6kA/m.The structure of sodium alginate-modified nano ferriferrous oxide granule as shown in Figure 1 in the magnetic liquid, the transmission electron microscope photo of the magnetic liquid that makes as shown in Figure 2, nano ferriferrous oxide average crystal grain particle diameter is approximately 7nm, and the average hydrodynamics radius of modified particles is about 45nm.
Embodiment 2
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 30% FeCl
3Solution, weighing 5g FeSO
4.7H
2O is made into mass concentration and is 15% FeSO
4Solution, all the other steps can obtain the magnetic liquid that the 50ml iron-holder is 3mg/ml with embodiment 1, and saturation magnetization is about 0.5kA/m.
Embodiment 3
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 45% FeCl
3Solution, weighing 5g FeSO
4.7H
2O is made into mass concentration and is 30% FeSO
4Solution, all the other steps can obtain the magnetic liquid that the 30ml iron-holder is 9mg/ml with embodiment 1, and saturation magnetization is about 1.6kA/m.
Embodiment 4
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution, all the other steps is with embodiment 1, the magnetic liquid that can to obtain about 30ml iron-holder be 10mg/ml, and saturation magnetization is about 1.8kA/m.
Embodiment 5
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 7g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution, all the other steps is with embodiment 1, the magnetic liquid that can to obtain about 30ml iron-holder be 9mg/ml, and saturation magnetization is about 1.6kA/m.
Embodiment 6
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 16g mean molecule quantity is that 20,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.All the other steps can obtain the magnetic liquid that the 20ml iron-holder is about 11mg/ml with embodiment 1, and saturation magnetization is about 1.9kA/m.
Embodiment 7
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 8g mean molecule quantity is that 20,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 60ml concentration is 25Wt%.All the other steps can obtain the magnetic liquid that the 10ml iron-holder is about 10mg/ml with embodiment 1, and saturation magnetization is about 1.8kA/m.
Embodiment 8
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 16g mean molecule quantity is that 50,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.All the other steps can obtain the magnetic liquid that the 5ml iron-holder is about 6mg/ml with embodiment 1, and saturation magnetization is about 0.9kA/m.
Embodiment 9
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 16g mean molecule quantity is that 10,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.All the other steps can obtain the magnetic liquid that the 35ml iron-holder is about 12mg/ml with embodiment 1, and saturation magnetization is about 1.8kA/m.
Embodiment 10
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 20g mean molecule quantity is that 20,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.Molysite mixed solution and sodium alginate ammoniacal liquor mixed solution are mixed under 400 rev/mins stirring, stir reaction down 60 minutes then, reaction temperature is stabilized in 80 ℃. and all the other steps are with embodiment 1.The magnetic liquid that can to obtain about 30ml iron-holder be 9mg/ml, saturation magnetization is about 1.3kA/m.
Embodiment 11
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 20g mean molecule quantity is that 20,000 sodium alginate is dissolved in and is made into sodium alginate ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.Molysite mixed solution and sodium alginate ammoniacal liquor mixed solution are mixed under 1800 rev/mins stirring, stir reaction down 40 minutes then, reaction temperature is stabilized in 50 ℃; All the other steps are with embodiment 1.The magnetic liquid that can to obtain about 30ml iron-holder be 9mg/ml, saturation magnetization is about 0.9kA/m.
Embodiment 12
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 5g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into molysite mixed solution, ferrous sulfate with two kinds of solution mixing: both mol ratios of ferric trichloride=1: 2.With the 20g weight average molecular weight is that 20,000 potassium alginate is dissolved in and is made into potassium alginate ammoniacal liquor mixed solution, at this moment ammoniacal liquor in the concentrated ammonia liquor that 100ml concentration is 25Wt%: the mol ratio of ferric trichloride is 40: 1, and carboxylated polysaccharide is 5: 1 to the mass ratio of tri-iron tetroxide.Molysite mixed solution and sodium alginate ammoniacal liquor mixed solution are mixed under 800 rev/mins stirring, stir reaction down 40 minutes then, reaction temperature is stabilized in 90 ℃; After reaction finishes, with centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, the bulky grain of removal precipitation, the even also stable dispersion of assurance nano ferriferrous oxide granule size is collected supernatant liquor as stable water base Fe 3 O 4 magnetic liquid in water.Adopt the method for cyclic washing ultrafiltration to remove unnecessary potassium alginate and foreign ion in the water-base magnetic liquid then, magnetic liquid being concentrated into iron-holder at last is 20mg/ml, and saturation magnetization reaches 3.5kA/m.
Embodiment 13
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 5g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into molysite mixed solution, ferrous sulfate with two kinds of solution mixing: both mol ratios of ferric trichloride=1: 2.With the 20g weight average molecular weight is that 20,000 alginic acid is dissolved in and is made into alginic acid ammoniacal liquor mixed solution, at this moment ammoniacal liquor in the concentrated ammonia liquor that 100ml concentration is 25Wt%: the mol ratio of ferric trichloride is 40: 1, and carboxylated polysaccharide is 5: 1 to the mass ratio of tri-iron tetroxide.Molysite mixed solution and alginic acid ammoniacal liquor mixed solution are mixed under 800 rev/mins stirring, stir reaction down 40 minutes then, reaction temperature is stabilized in 90 ℃; After reaction finishes, with centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, the bulky grain of removal precipitation, the even also stable dispersion of assurance nano ferriferrous oxide granule size is collected supernatant liquor as stable water base Fe 3 O 4 magnetic liquid in water.Adopt the method for gel chromatography to remove unnecessary sodium alginate and foreign ion in the water-base magnetic liquid then, magnetic liquid being concentrated into iron-holder at last is 20mg/ml, and saturation magnetization reaches 3.5kA/m.
Embodiment 14
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.With the 16g mean molecule quantity is that 20,000 Sensor Chip CM 5 is dissolved in and is made into Sensor Chip CM 5 ammoniacal liquor mixed solution in the concentrated ammonia liquor that 80ml concentration is 25Wt%.Molysite mixed solution and Sensor Chip CM 5 ammoniacal liquor mixed solution are mixed under 800 rev/mins stirring, stir reaction down 40 minutes then, reaction temperature is stabilized in 99 ℃; After reaction finishes, with centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, the bulky grain of removal precipitation, the even also stable dispersion of assurance nano ferriferrous oxide granule size is collected supernatant liquor as stable water base Fe 3 O 4 magnetic liquid in water.Adopt the method for cyclic washing ultrafiltration to remove unnecessary sodium alginate and foreign ion in the water-base magnetic liquid then, magnetic liquid being evaporated to iron-holder at last is 30mg/ml, and saturation magnetization reaches 5kA/m.
Embodiment 15
Get 9.6g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution, weighing 4g FeCl
2.4H
2O is made into mass concentration and is 20% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.All the other steps are with embodiment 1.The magnetic liquid that can to obtain about 30ml iron-holder be 9mg/ml, saturation magnetization is about 1.8kA/m.
Embodiment 16
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 60% FeCl
3Solution is got 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, at this moment ferrous sulfate: ferric trichloride: ammoniacal liquor three's mol ratio=1.2: 2: 16, reaction under agitation, regulating rotating speed is 800 rev/mins, and keep reaction temperature about 60 ℃, reacted 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 30 μ s/cm ultrasonic then dispersion 2 minutes.In 100ml concentration is the sodium alginate of the tri-iron tetroxide solution adding 0.4g weight average molecular weight 20,000 of 0.4g/100ml, regulation system pH to 4.5, continuous stirring 40min in 60 ℃ of water-baths; Question response washes repeatedly and is settled to 40ml with water after finishing, and the conductivity of reaction system is reduced to less than 30 μ s/cm, and the pH value is between 6.5～7.5, and last sonicated 2 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is 1.5kA/m, and the transmission electron microscope photo of magnetic liquid as shown in Figure 3.
Embodiment 17
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 30% FeCl
3Solution is got 6g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1200 rev/mins, and keeps reaction temperature about 60 ℃, reacts 20 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is approximately 1.6kA/m.
Embodiment 18
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 6g FeSO
4.7H
2O is made into mass concentration and is 5% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1800 rev/mins, and keeps reaction temperature about 60 ℃, reacts 10 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is 1.6kA/m.
Embodiment 19
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 5% FeCl
3Solution is got 5g FeSO
4.7H
2O is made into mass concentration and is 2.5% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 15ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 400 rev/mins, and keeps reaction temperature about 30 ℃, reacts 10 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 9mg/ml, and saturation magnetization is 0.8kA/m.
Embodiment 20
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 20% FeCl
3Solution is got 5g FeSO
4.7H
2O is made into mass concentration and is 20% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 10ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1200 rev/mins, and keeps reaction temperature about 60 ℃, reacts 20 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is 0.8kA/m.
Embodiment 21
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 7g FeSO
4.7H
2O is made into mass concentration and is 10% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 800 rev/mins, and keeps reaction temperature about 60 ℃, reacts 20 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is 1.2kA/m.
Embodiment 22
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 4g FeCl
2.4H
2O is made into mass concentration and is 10% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1500 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 9mg/ml, and saturation magnetization is 1.3kA/m.
Embodiment 23
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 5% FeCl
3Solution is got 4.6g FeCl
2.4H
2O is made into mass concentration and is 2.5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 800 rev/mins, and keeps reaction temperature about 60 ℃, reacts 20 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 9mg/ml, and saturation magnetization is 1.5kA/m.
Embodiment 24
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 5.6g FeCl
2.4H
2O is made into mass concentration and is 5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1000 rev/mins, and keeps reaction temperature about 45 ℃, reacts 30 minutes.All the other steps are with embodiment 15.The magnetic liquid iron-holder reaches 8mg/ml, and saturation magnetization is 1.4kA/m.
Embodiment 25
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 6g FeSO
4.7H
2O is made into mass concentration and is 5% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 20 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 80 μ s/cm ultrasonic dispersion 5 minutes.In 100ml concentration is the sodium alginate of the tri-iron tetroxide solution adding 2g weight average molecular weight 20,000 of 1g/100ml, regulation system pH to 5.5, continuous stirring 30min in 60 ℃ of water-baths; Question response washes repeatedly and is settled to 40ml with water after finishing, and the conductivity of reaction system is reduced to less than 70 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic dispersion 3 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 20mg/ml, and saturation magnetization is 3.2kA/m.
Embodiment 26
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 6g FeSO
4.7H
2O is made into mass concentration and is 10% FeSO
4Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 30 μ s/cm ultrasonic then dispersion 4 minutes.In 100ml concentration is the potassium alginate of the tri-iron tetroxide solution adding 0.5g weight average molecular weight 20,000 of 1g/100ml, regulation system pH to 5, continuous stirring 40min in 80 ℃ of water-baths; Question response washes repeatedly and is settled to 20ml with water after finishing, and the conductivity of reaction system is reduced to less than 30 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic then dispersion 3 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 30mg/ml, and saturation magnetization is 5kA/m.
Embodiment 27
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 4.6g FeCl
2.4H
2O is made into mass concentration and is 5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 80 μ s/cm ultrasonic then dispersion 2 minutes.In 100ml concentration is the alginic acid of the tri-iron tetroxide solution adding 0.25g weight average molecular weight 20,000 of 1g/100ml, regulation system pH to 4.5, continuous stirring 60min in 50 ℃ of water-baths; Question response washes repeatedly and is settled to 40ml with water after finishing, and the conductivity of reaction system is reduced to less than 20 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic dispersion 2 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 15mg/ml, and saturation magnetization is 2.5kA/m.
Embodiment 28
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 4.6g FeCl
2.4H
2O is made into mass concentration and is 5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 20 μ s/cm ultrasonic then dispersion 2 minutes.In 100ml concentration is the Sensor Chip CM 5 of the tri-iron tetroxide solution adding 0.5g weight average molecular weight 20,000 of 1g/100ml, regulation system pH to 3, continuous stirring 45min in 80 ℃ of water-baths; Question response washes repeatedly and is settled to 20ml with water after finishing, and the conductivity of reaction system is reduced to less than 20 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic dispersion 2 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 40mg/ml, and saturation magnetization is 8kA/m.
Embodiment 29
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 4.6g FeCl
2.4H
2O is made into mass concentration and is 5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 30 μ s/cm ultrasonic then dispersion 2 minutes.In 100ml concentration is the Sensor Chip CM 5 sodium of the tri-iron tetroxide solution adding 0.5g weight average molecular weight 50,000 of 1g/100ml, regulation system pH to 3, continuous stirring 45min in 75 ℃ of water-baths; Question response washes repeatedly and is settled to 20ml with water after finishing, and the conductivity of reaction system is reduced to less than 30 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic dispersion 2 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 30mg/ml, and saturation magnetization is 4kA/m.
Embodiment 30
Weighing 9.5g FeCl
3.6H
2O is made into mass concentration and is 10% FeCl
3Solution is got 4.6g FeCl
2.4H
2O is made into mass concentration and is 5% FeCl
2Solution is made into the molysite mixed solution with two kinds of solution mixing.Adding molysite mixed solution and 20ml concentration simultaneously is the ammoniacal liquor of 25Wt%, high-speed stirred, and regulating rotating speed is 1300 rev/mins, and keeps reaction temperature about 60 ℃, reacts 30 minutes.Reaction finishes the back and add 100ml distilled water in stirring condition downhill reaction system, low whipping speed continues down for 400 rev/mins to stir 3 minutes, adopt magnetic support sedimentation separation nanometer Fe 3 O 4 magnetic particle and supernatant liquor, carry out repeatedly repeatedly, making concentration is that the conductivity of the tri-iron tetroxide solution of 0.4g/100ml is reduced to less than 30 μ s/cm ultrasonic then dispersion 2 minutes.In 100ml concentration is the potassium alginate of the tri-iron tetroxide solution adding 0.5g weight average molecular weight 10,000 of 1g/100ml, regulation system pH to 4.5, continuous stirring 45min in 75 ℃ of water-baths; Question response washes repeatedly and is settled to 20ml with water after finishing, and the conductivity of reaction system is reduced to less than 30 μ s/cm, and the pH value is between 6.5～7.5, and ultrasonic dispersion 2 minutes makes water base Fe
3O
4Magnetic liquid.The magnetic liquid iron-holder reaches 35mg/ml, and saturation magnetization is 5kA/m.
Claims (7)
1. a water-base magnetic liquid mainly is made up of nano ferriferrous oxide granule, stabilizer and water, it is characterized in that described stabilizer is a carboxylated polysaccharide, and the weight average molecular weight of carboxylated polysaccharide is between 10,000～20,000.
2. water-base magnetic liquid according to claim 1 is characterized in that described carboxylated polysaccharide is a kind of in the alkali metal salt of alginic acid or alginic acid.
3. water-base magnetic liquid according to claim 1 is characterized in that described carboxylated polysaccharide is a kind of in the alkali metal salt of Sensor Chip CM 5, Sensor Chip CM 5.
4. a method for preparing the described water-base magnetic liquid of claim 1 is characterized in that adopting one-step technology, and promptly the chemical coprecipitation in the presence of stabilizer prepares water-base magnetic liquid, may further comprise the steps:
1. there is synthesis of nano ferriferrous oxide particles down in carboxylated polysaccharide
It is 30%～65% the aqueous solution that ferric trichloride is made into mass concentration, it is 15%～30% the aqueous solution that ferrous chloride or ferrous sulfate are mixed with mass concentration, by ferrous chloride or ferrous sulfate: both mol ratios of ferric trichloride are 1.0～1.4: 2 proportionings, two kinds of solution mixing are made into the molysite mixed solution, carboxylated polysaccharide is dissolved in the concentrated ammonia liquor of 25Wt%～30Wt% and is made into carboxylated polysaccharide ammoniacal liquor mixed solution, by ammoniacal liquor: the mol ratio of ferric trichloride is 12～40: 1, carboxylated polysaccharide is 2～5: 1 ratio to the mass ratio of tri-iron tetroxide, molysite mixed solution and carboxylated polysaccharide ammoniacal liquor mixed solution are under agitation mixed, under agitation reacted then 20～60 minutes, mixing speed is controlled at 300～1800 rev/mins, reaction temperature is controlled between 50～99 ℃, obtains containing unstable oarse-grained water base Fe 3 O 4 magnetic liquid;
2. unsettled bulky grain is removed in centrifugation
With centrifuge prepared water base Fe 3 O 4 magnetic liquid is made centrifugal treating, the bulky grain of removal precipitation, the even also stable dispersion of assurance nano ferriferrous oxide granule size is collected supernatant liquor as stable water-base magnetic liquid in water.
5. the preparation method of water-base magnetic liquid according to claim 4 is characterized in that described reaction temperature is controlled between 90～99 ℃.
6. a method for preparing the described water-base magnetic liquid of claim 1 is characterized in that adopting two-step process, promptly adopts chemical coprecipitation to prepare nano ferriferrous oxide granule earlier, carries out surface modification then and prepares water-base magnetic liquid, may further comprise the steps:
1. nano ferriferrous oxide granule is synthetic
It is 2%～65% the aqueous solution that ferric trichloride is made into mass concentration, it is 1%～30% the aqueous solution that ferrous chloride or ferrous sulfate are mixed with mass concentration, by ferrous chloride or ferrous sulfate: both mol ratios of ferric trichloride are that 1.0～1.4: 2 proportionings are mixed two kinds of solution and are made into the molysite mixed solution, by ferrous chloride or ferrous sulfate: ferric trichloride: ammoniacal liquor three's mol ratio is 1.0～1.4: 2: 8～16 proportionate relationship, the concentrated ammonia liquor that under agitation adds molysite mixed solution and 25Wt%～30Wt% simultaneously, mixing speed is controlled at 400～2000 rev/mins, reaction temperature is stabilized between 30～60 ℃, reacted 10～30 minutes, and obtained the nanometer Fe 3 O 4 magnetic particle;
2. the washing of nano ferriferrous oxide granule and ultrasonic dispersion
With the distilled water nanometer Fe 3 O 4 magnetic particle that obtains of cleaning reaction repeatedly, making concentration is that the conductivity of the ferroferric oxide gel solution of 0.3～1g/100ml is reduced to less than 100 μ s/cm ultrasonic then dispersion 1～5 minute;
3. nano ferriferrous oxide granule surface modification and the dispersion in water
Concentration be in the ferroferric oxide gel solution of 0.3～1g/100ml by tri-iron tetroxide: both mass ratioes of carboxylated polysaccharide are 1: 0.25～2 to add carboxylated polysaccharides, regulate between this system pH to 3～6, continuous stirring 30～60 minutes is reflected in 50～80 ℃ of water-baths and carries out; After question response finishes, wash with water repeatedly, make that to contain tri-iron tetroxide concentration be that the conductivity of the reaction system of 0.4～4g/100ml is reduced to less than 100 μ s/cm, the pH value is between 6.5～7.5, ultrasonic then dispersion 1～5 minute makes water base Fe 3 O 4 magnetic liquid.
7. the preparation method of water-base magnetic liquid according to claim 6 is characterized in that the conductivity of ferroferric oxide gel solution described in step 2. is reduced to less than 30 μ s/cm.
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| CN103342392B (en) * | 2013-06-25 | 2015-11-18 | 升华集团德清华源颜料有限公司 | A kind of magnetic oxygenated iron oxide black |
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| JPH09227216A (en) * | 1996-02-20 | 1997-09-02 | Asahi Tec Corp | Production of porous magnetized base material |
| CN1477082A (en) * | 2003-07-11 | 2004-02-25 | 吉林大学 | Method for preparing ferrite/silicon dioxide core-shell nano particles by using ultrasonic treatment |
| CN1555910A (en) * | 2004-01-07 | 2004-12-22 | 中山大学 | N-acyl sarcosine modified aqueous magnetic liquid and its preparation method |
| CN1595558A (en) * | 2004-06-22 | 2005-03-16 | 上海大学 | A magnetic rheological fluid and preparing method thereof |
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| JPH09227216A (en) * | 1996-02-20 | 1997-09-02 | Asahi Tec Corp | Production of porous magnetized base material |
| CN1477082A (en) * | 2003-07-11 | 2004-02-25 | 吉林大学 | Method for preparing ferrite/silicon dioxide core-shell nano particles by using ultrasonic treatment |
| CN1555910A (en) * | 2004-01-07 | 2004-12-22 | 中山大学 | N-acyl sarcosine modified aqueous magnetic liquid and its preparation method |
| CN1595558A (en) * | 2004-06-22 | 2005-03-16 | 上海大学 | A magnetic rheological fluid and preparing method thereof |
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