CN101154493A - Superparamagnetism microsphere and method for manufacturing the same - Google Patents
Superparamagnetism microsphere and method for manufacturing the same Download PDFInfo
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Abstract
The invention relates to a superparamagnetism microballoon sphere and a preparation method of the same. Under the circumstance of the protection of vacuum or nitrogen at the room temperature, a microballoon sphere with a plurality of holes or a hollow structure is dipped in metallic ion solution to rotate and vaporize, and then ammonia or standard caustic is added into the prior metallic ion solution to mix and react, the magnetic field separates magnetic microballoon spheres with a plurality of holes or a hollow structure to be cleaned, surface active agent of isopropanol and ammonia as well as ethyl orthosilicate are added, and superparamagnetism microballoon sphere wrapped with silicon dioxide is obtained. Fundamental groups with multiple functions can be assembled on the surface of the microballoon sphere selectively. The inner holes of the microballoon sphere have good compatibility with the metallic ions, and the magnetic nanometer particles are evenly distributed. Therefore, the superparamagnetism microballoon sphere is of good superparamagnetism and chemical and physical stability, acid resistance and alkali resistance, low possibility of oxidation or glomeration. The invention is of simple art, small number of equipment, convenient control, high output capacity, low cost of production and easiness of mass production.
Description
Affiliated technical field
The present invention relates to a kind of magnetic organic-inorganic hybrid material and preparation method thereof, is a kind of organic inorganic hybridization superparamagnetism microballoon and preparation method thereof specifically.
Background technology
Magnetic macromolecular microsphere as novel functional high molecule material biomedical as clinical diagnosis, the enzyme mark, targeted drug, cytology such as cell marking, cell separation etc., with the fields such as immobilization of bioengineering such as enzyme very application prospects is arranged, the scholar who abroad has is called power particle (dynabead) with its image.Polymer microballoon how to prepare monodispersed superparamagnetism is an important research field of chemistry and material science.
The method of prior art synthesizing magnetic polymer composite microsphere mainly contains the macromolecule investment, chemical conversion and monomer polymerization method.Wherein the macromolecule investment prepares magnetic microsphere, and method is simple, but the gained particle size distribution is wide, out-of-shape, particle diameter is wayward, mixes some impurity such as emulsifying agent in the shell unavoidably, be applied to immunoassays, fields such as cell separation can be very limited.Though the microballoon that chemical transformation synthesizes is functional, but satisfy various requirement, but technology is too complicated.The monomer polymerization method of synthesizing magnetic microballoon comprises suspension polymerization, dispersion copolymerization method, emulsion polymerization (no soap, the seed law) etc.Adopt the key of this method to be that the polymerization reaction of monomer carries out the consistency problem with inorganic hydrophilic magnetic-particle and organic lipophile vinyl monomer smoothly on the magnetic-particle surface.
Now common relevant polymerization is heat initiation vinyl monomer polymerization in the presence of the stable magnetic fluid of surfactant, the difficult on the one hand synthetic large grain size magnetic polymer microballoon of this method, because differing, the lipophile vinyl monomer establishes a capital polymerization around the magnetic ferroferric oxide particle on the other hand, cause synthetic microballoon magnetic ferroferric oxide granule content wayward, ferriferrous oxide particles is agglomerated into bulk in the ball, become heterogeneous structure, how much inhomogeneous magnetic content is between ball and the ball, even some microballoon is nonmagnetic, and the finished product output capacity is low etc.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of technology stability, the preparation method of the high and microballs of super-paramagnetic polymer that is evenly distributed of magnetic content, and provide a kind of superparamagnetism good, magnetic content height, be difficult for reuniting, acid-fast alkali-proof, physical and chemical performance is stable, is easy to adhere to the superparamagnetism microballoon of multiple functional groups on its surface.
Technical solution of the present invention is: a kind of superparamagnetism method for preparing microsphere may further comprise the steps:
A. preparing metal solion;
B. under vacuum or nitrogen protection and room temperature condition, the porous of drying or hollow microsphere were soaked in the metal ion solution 18-24 hour, then in vacuum or nitrogen protection, rotary evaporation under the 20-60 degrees celsius, moisture content volatilizees fully in metal ion solution;
C. porous after evaporation or hollow microsphere add 30-50 degree centigrade ammoniacal liquor or sodium hydroxide solution, control pH value 9-11 is warming up to 60-90 degree centigrade, stirring reaction 10-50 minute, leave standstill and be cooled to room temperature, under the action of a magnetic field, from solution, isolate porous or hollow magnetic microsphere;
D. with porous or hollow microsphere alcohol wash clean, in porous or hollow microsphere and surfactant mass ratio 1: 1-1: 5 ratio adds the surfactant Tween-20, in porous or hollow microsphere and isopropyl alcohol mass ratio 1: 15-1: 20 ratio adds the solvent isopropyl alcohol, adding acidity value by general consumption is ammoniacal liquor or the hydrochloric acid of 1-4, add tetraethoxysilane at last, soak after 30-50 minute, extremely neutral with deionized water wash, oven dry, the superparamagnetism microballoon that obtains being coated with silicon oxide.
The inventive method can also adopt ferric trichloride (FeCl in described steps A
36H
2O), the ferrous (FeCl of dichloride
24H
2O) and aluminum nitrate (Al (NO3)
39H
2O) preparing metal deionized water solution, the ferrous ion (Fe in the described metal ion aqueous solution
2+) and ferric ion (Fe
3+) mol ratio be 1: 2-1: 0, aluminium ion amount and ferrous ion (Fe
2+), ferric ion (Fe
3+) mol ratio of both sums is 1: 0.1-1: 1.5; Perhaps by stoichiometric proportion weighing cobalt nitrate (Co (NO
3)
26H
2O), nickel nitrate (Ni (NO
3)
26H
2O), ferric nitrate (Fe (NO3)
39H
2O), wherein concentration ratio is divalent cobalt ion/bivalent nickel ion/ferric ion/hydroxide ion=1/1/2/30 (Co
2+/ Ni
2/
+Fe
3+/ OH
-=1/1/2/30) unit is every liter of a mole, respectively obtain solution and mix and become metal ion solution.
The preparation method of porous or hollow microsphere is as follows among the described step B of the inventive method:
B1) prepare polymeric dispersant under nitrogen protection, described dispersant is polyacrylic acid or polymethylacrylic acid or polyacrylamide or poly N-vinyl pyrrolidone solution, and the monomer of polymerization is a styrene, and the mass ratio of monomer and dispersant is 8: 1～12: 1;
B2) distilled water, absolute ethyl alcohol, dispersant and styrene are added in the container respectively stir, slowly be warming up to 60-80 degree centigrade, add initator azodiisobutyronitrile or dibenzoyl peroxide, isothermal reaction 15-30 hour, cooling discharging, the reactant centrifugation is also used methanol wash, obtain polymer microballoon after the drying;
B3) above-mentioned polymer microballoon is packed into filter paper bag is put into cable-styled extractor, adds dichloromethane solution, and solution is heated to 40-80 degree centigrade, and the linear polymer 1-4 in the extracting polymer microballoon hour, cooling obtained porous or hollow microsphere after the drying.
Among the described step B of the inventive method, add porous or hollow microsphere in the cucurbit on Rotary Evaporators, earlier pre-exhaust, and feed nitrogen adds metal ion solution, bleeds once more and feeds nitrogen, is rotated evaporation then.
Among the described step D of the inventive method, in the mass ratio 1 of porous or hollow microsphere and tetraethoxysilane: 1-1: 4 ratio adds tetraethoxysilane.
Another purpose technical solution of the present invention is: a kind of superparamagnetism microballoon, at porous or the hollow microsphere interior polymeric ion that is magnetic, layer is coated with silicon oxide on the surface of porous or hollow microsphere.
Porous of the present invention or hollow microsphere adopt distilled water, absolute ethyl alcohol, dispersant and styrene polymerization to form.
The invention has the beneficial effects as follows:
1. the polymer microballoon that dispersin polymerization is formed, extracting goes out linear polymer, and the space of resultant porous or hollow microsphere is bigger, particle diameter is even, balling-up is good, the size homogeneous, and the polymer belt of the small-molecular weight of the hole inner wall surface of microballoon have functional group (as-COOH ,-NH
2Deng), this class group is easy to combine with metallic ion coordination, thereby last magnetic thing adhesion effect is good, magnetic content height, and magnetic thing distribution homogeneous, physical and chemical performance are stable.
2. under vacuum or nitrogen protection environment; adopt the mode of rotary evaporation to soak into the generation magnetic particle; avoid taking place oxidation reaction; guarantee that magnetic nanoparticle is evenly distributed in the microballoon; and can control the content of magnetic particle by the concentration of infiltrate; the high conformity of magnetic-particle and microballoon quality guarantees to have good superparamagnetism.
3. behind the coated silica, can keep the chemical physical stability of magnetic microsphere effectively, be not easy oxidation, be not easy to reunite, the acid and alkali resistance performance is good.
4. the inventive method technology is simple, and equipment needed thereby is few, and control is convenient, the output capacity height, and the magnetic content height of microballoon has superparamagnetism preferably, and production cost is low, is easy to tissue and produces in enormous quantities.
Description of drawings
Fig. 1 is ordinary optical microscope (* 100) picture that the inventive method prepares the superparamagnetism microballoon
Fig. 2 is ordinary optical microscope (* 1000) picture that the inventive method prepares the superparamagnetism microballoon
Fig. 3 is the infrared spectrum analysis figure before and after cleaning behind the superparamagnetism microballoon coated silica of the present invention
Fig. 4 is the magnetic hysteresis loop figure before and after the superparamagnetism microballoon coated silica of the present invention
Embodiment
The present invention is described in further detail below in conjunction with description of drawings and embodiment:
1. superparamagnetism method for preparing microsphere may further comprise the steps:
A. preparing metal solion;
B. under vacuum or nitrogen protection and room temperature condition, the porous of drying or hollow microsphere were soaked in the metal ion solution 18-24 hour, then in vacuum or nitrogen protection, rotary evaporation under the 20-60 degrees celsius, moisture content volatilizees fully in metal ion solution;
C. porous after evaporation or hollow microsphere add 30-50 degree centigrade ammoniacal liquor or sodium hydroxide solution, control pH value 9-11 is warming up to 60-90 degree centigrade, stirring reaction 10-50 minute, leave standstill and be cooled to room temperature, under the action of a magnetic field, from solution, isolate porous or hollow magnetic microsphere;
D. with porous or hollow microsphere alcohol wash clean, in porous or hollow microsphere and surfactant mass ratio 1: 1-1: 5 ratio adds the surfactant Tween-20, in porous or hollow microsphere and isopropyl alcohol mass ratio 1: 15-1: 20 ratio adds the solvent isopropyl alcohol, the ammoniacal liquor or the hydrochloric acid that add certain pH value by general consumption, add tetraethoxysilane at last, soak after 30-50 minute, extremely neutral with deionized water wash, oven dry, the superparamagnetism microballoon that obtains being coated with silicon oxide.
Adopt in the described steps A of the inventive method with ferric trichloride (FeCl
36H
2O), the ferrous (FeCl of dichloride
24H
2O) and aluminum nitrate (Al (NO3)
39H
2O) preparing metal solion, the ferrous ion (Fe in the described metal ion solution
2+) and ferric ion (Fe
3+) mol ratio be 1: 2-1: 0, aluminum nitrate (Al (NO3)
39H
2O) with ferrous ion (Fe
2+), ferric ion (Fe
3+) mol ratio of both sums is 1: 0.1-1: 1.5; Perhaps by stoichiometric proportion weighing cobalt nitrate (Co (NO
3)
26H
2O), nickel nitrate (Ni (NO
3)
26H
2O), ferric nitrate (Fe (NO3)
39H
2O), wherein concentration ratio is divalent cobalt ion/bivalent nickel ion/ferric ion/hydroxide ion=1/1/2/30 (Co
2+/ Ni
2 +/ Fe
3+/ OH
-=1/1/2/30), unit is every liter of a mole, respectively obtain solution and mix and become metal ion solution.
The preparation method of porous or hollow microsphere is as follows among the described step B of the inventive method:
B1) prepare polymeric dispersant under nitrogen protection, described dispersant is polyacrylic acid or polymethylacrylic acid or polyacrylamide or poly N-vinyl pyrrolidone solution, and the monomer of polymerization is a styrene, and the mass ratio of monomer and dispersant is 8: 1～12: 1;
B2) distilled water, absolute ethyl alcohol, dispersant and styrene are added in the container respectively stir, slowly be warming up to 60-80 degree centigrade, add initator azodiisobutyronitrile or dibenzoyl peroxide, isothermal reaction 15-30 hour, cooling discharging, the reactant centrifugation is also used methanol wash, obtain polymer microballoon after the drying;
B3) above-mentioned polymer microballoon is packed into filter paper bag is put into cable-styled extractor, adds dichloromethane solution, solution is heated to 40 degrees centigrade-80 degrees centigrade, linear polymer 1-4 in the extracting polymer microballoon hour, cooling obtained porous or hollow microsphere after the drying.
Among the described step B of the inventive method, add porous or hollow microsphere in the cucurbit on Rotary Evaporators, earlier pre-exhaust, and feed nitrogen adds metal ion solution, bleeds once more and feeds nitrogen, is rotated evaporation then.
Among the described step D of the inventive method, in the mass ratio 1 of porous or hollow microsphere and tetraethoxysilane: 1-1: 4 ratio adds tetraethoxysilane.
A kind of superparamagnetism microballoon of the present invention, at porous or the hollow microsphere interior polymeric ion that is magnetic, layer is coated with silicon oxide on the surface of porous or hollow microsphere.
Described porous or hollow microsphere adopt distilled water, absolute ethyl alcohol, dispersant and styrene polymerization to form.
Embodiment 1: the polymeric dispersant of utilization solution polymerization small-molecular weight
Polymerization reaction is being equipped with reflux condensing tube, stirs, and carries out in the there-necked flask of feeding device and under nitrogen protection, and the reaction temperature control is about 60 degrees centigrade.Add 150 ml waters successively, 5 milliliters of acrylic acid, constant temperature stirred after 10-15 minute in 250 milliliters of there-necked flasks of 1 gram sodium chloride adding, add 5 milliliters of mass fractions gradually and be 5% the initiator potassium persulfate aqueous solution, polymerization reaction begins, and reacts cooling 10-15 hour, alcohol water cleans removes sodium chloride three times, obtains stable polyacrylic acid latex solution.Also can adopt above-mentioned typical dispersion copolymerization method, prepare polymethylacrylic acid or dispersant solution such as polyacrylamide or poly N-vinyl pyrrolidone.
Embodiment 2: the utilization dispersion copolymerization method prepares monodisperse polymer micro-sphere
Polyacrylic acid latex solution among redistilled water, absolute ethyl alcohol, the embodiment 1 and styrene are added respectively in 250 milliliters of there-necked flasks that have blender, thermometer and condenser, charge into nitrogen, under the nitrogen protection condition, open and stir; Slowly heat up, reach 70-80 degree centigrade after, add azodiisobutyronitrile and begin reaction, after isothermal reaction 18-24 hour, cooling discharging.Fully wash with the polymeric articles centrifugation and with methyl alcohol, drying obtains polymer microballoon.Wherein distinctive recipe ratio is: cinnamic ratio accounts for 10.03% of oeverall quality, and absolute ethyl alcohol accounts for oeverall quality 68.56%, and redistilled water accounts for oeverall quality 20.4%, and azodiisobutyronitrile accounts for 1.68% of monomer, and polyacrylic acid accounts for 11.99% of monomer.Dispersant in the present embodiment also can adopt the polymeric dispersant of polymethylacrylic acid or small-molecular weights such as polyacrylamide or poly N-vinyl pyrrolidone.
Embodiment 3: the extracting of utilization Soxhlet extractor goes out the linear polymer in the polymer microballoon
Adopt XT-06 type Soxhlet extractor in the test, the a certain amount of polymer microballoon of the getting embodiment 2 preparation good little filter paper bag of prepared beforehand of packing into, put into extractor, the solution that extracting is used is carrene, the dichloromethane solution heated temperatures is 40-60 degree centigrade, the extracting time is 1-2 hour, and extracting intact back oven dry obtains porous or hollow microsphere.After extracting, the polymer belt that solution leaves small-molecular weight in porous or hollow microsphere hole inner wall surface have functional group (as-COOH ,-NH
2Deng) structure sheaf, be easy to combine with metallic ion coordination.
Embodiment 4: metal ion is soaked in the porous microsphere, and prepare magnetic nanoparticle
In the solution that the porous or the hollow microsphere of embodiment 3 preparation is immersed in metal organic salt; soak under the room temperature and made in 18-24 hour in the hole and hole that metal organic salt fully enters porous or hollow microsphere; then at solution temperature 20-60 degree centigrade; under vacuum or the nitrogen protection condition, adopt the Rotary Evaporators rotary evaporation.Add porous or hollow microsphere in can the cucurbit on Rotary Evaporators, earlier pre-exhaust, and feed nitrogen adds the metal organic salt aqueous solution, bleeds once more and feeds nitrogen, is rotated evaporation then.The representative formula of preparing metal organic slat solution wherein: ferric trichloride is (FeCl
36H
2O) 2.2-4.6 gram, ferrous chloride (FeCl
24H
2O) be 0.8-1.7 gram, aluminum nitrate (Al (NO3)
39H
2O) be the 0.46-0.92 gram.Also can be by stoichiometric proportion weighing cobalt nitrate (Co (NO
3)
26H
2O), nickel nitrate (Ni (NO
3)
26H
2O), ferric nitrate (Fe (NO3)
39H
2O), wherein concentration ratio is divalent cobalt ion/bivalent nickel ion/ferric ion/hydroxide ion=1/1/2/30 (Co
2+/ Ni
2/
+Fe
3+/ OH
-=1/1/2/30), unit is every liter of a mole, and obtain solution and mix and become metal ion solution is used to soak porous or hollow microsphere respectively.
After porous or hollow microsphere rotary evaporation finished, acidity value 9-11 in temperature is 30-50 degree centigrade of following dropping ammonia or sodium hydroxide solution and control bottle was warming up to 70-80 degree centigrade after dripping, stirring reaction, and mechanical agitation speed is 100-200rpm; React after 10-50 minute, take out cooling and leave standstill, under the action of a magnetic field, from solution, isolate porous or hollow magnetic microsphere.
In the present embodiment, also can use the porous or the hollow microsphere of other method preparation at present.
Embodiment 5: be that template is at microsphere surface coated silica layer with the microballoon
At first that the porous or the hollow magnetic microsphere of embodiment 4 preparations is clean with the alcohol washing, add the surfactant Tween-20, add the solvent isopropyl alcohol again, drip catalyst ammonia water or hydrochloric acid, the presoma tetraethoxysilane that adds silicon dioxide, stirring at room twenty four hours simultaneously makes the porous or the hollow magnetic microsphere of coated silica layer.Activating agent Tween-20 wherein: 5-10 milliliter, mass fraction are 0.5%, isopropyl alcohol: the 16-20 milliliter, ammoniacal liquor: 0.4-1 milliliter, mass fraction are 25%, tetraethoxysilane: 0.04-1 milliliter, the thickness of the amount decision silicon dioxide layer of tetraethoxysilane.
Leave standstill twenty four hours after having reacted, the direct vacuumize of the sample that takes a morsel also is the curve of spectrum 1 among Fig. 3 with infrared spectrogram that bromination sylvite mixing compressing tablet records sample, remaining respectively giving a baby a bath on the third day after its birth with alcohol and water is inferior, vacuumize, the infrared spectrogram that records sample with bromination sylvite mixing compressing tablet that takes a morsel is the curve of spectrum 2 among Fig. 3.
Referring to Fig. 1, Fig. 2 is by the magnetic microsphere pattern rule of the inventive method preparation, even particle size distribution, the about 1-5 micron of granularity.The magnetic nano-particle disperse is distributed in the microballoon, and mainly concentrates on the microballoon cavity inner wall, and is dispersed and better with the affinity effect of microballoon inner wall surface.
Referring to Fig. 3, curve 1 is the curve of spectrum of magnetic microsphere when not cleaning behind the coated silica, and curve 2 is the curves of spectrum after cleaning behind the coated silica and to magnetic microsphere, and microballoon is at 543cm
-1Absworption peak corresponding to Fe
3O
4Characteristic absorption, 1024,1097 and 3000cm
-1Near 5 characteristic absorption are corresponding to polystyrene.1100cm
-1The absworption peak of the corresponding O-Si-O of strong absorption near, microsphere surface has coated silicon dioxide as can be seen from Figure 3.
Referring to Fig. 4, the magnetic hysteresis loop figure before and after magnetic microsphere coated silica of the present invention, curve 3 is the magnetic hysteresis loops before the coated silica, curve 4 is the magnetic hysteresis loops behind the coated silica, article two, " area " that magnetic hysteresis loop surrounded all is zero, and this just can illustrate that the magnetic microsphere finished product has good superparamagnetism.
After testing, the superparamagnetism microballoon of the inventive method preparation has following characteristics:
1) have superparamagnetism, magnetic particle is evenly distributed, and stable fine after the dispersion magnetic can not take place in the use The property reunion, be easy to disperse, works very well under sour environment, cost is low, the product purity height.
2) polymer microballoon magnetic content is even, and the output capacity height is about 90%, and particle size is in 0.5～20 micrometer range Size is controlled, and particle diameter is even, can be as requested changes between 2～10 microns, and magnetic Fe_3O_4 accounts for whole microballoon Percentage by weight is between the 0.5-60%. Physico-chemical property is stable, at 0.1 mole of every liter of hydrochloric acid and 0.1 mole of every liter of hydrogen-oxygen Change in the sodium water solution substantially unchanged about one week of immersion. And the microballoon of additive method preparation is at 0.1 mole of every liter of hydrochloric acid water Immersion became yellow green in about 3 days in the solution, soaked meeting in about 3 days at 0.1 mole of every liter of sodium hydrate aqueous solution and occurred Coacervation, this may be because due to macromolecular material degrades.
3) microballs of super-paramagnetic polymer also can be by copolymerization except having the characteristic of high molecular composite microsphere, and the surface changes The property processing, give its multiple reactive functional group in surface, such as-OH ,-COOH ,-CHO ,-NH2 etc., microsphere surface Functional group can optionally be assembled up, has diversity and controllability, can produce in enormous quantities; And institute of the present invention State the group content of microballoon assembling function group rear surface up to 0.2 mM of every gram even more, and side before this The most of functional group of the made microballoon of method is positioned at microballoon inside, and surperficial content is few, only be about 0.1 mM of every gram even Still less; Also because have superparamagnetism, can under externally-applied magnetic field, separate easily.
Claims (7)
1. superparamagnetism method for preparing microsphere is characterized in that may further comprise the steps:
A. preparing metal solion;
B. under vacuum or nitrogen protection and room temperature condition, the porous of drying or hollow microsphere were soaked in the metal ion solution 18-24 hour, then in vacuum or nitrogen protection, rotary evaporation under the 20-60 degrees celsius, moisture content volatilizees fully in metal ion solution;
C. porous after evaporation or hollow microsphere add 30-50 degree centigrade ammoniacal liquor or sodium hydroxide solution, control pH value 9-11 is warming up to 60-90 degree centigrade, stirring reaction 10-50 minute, leave standstill and be cooled to room temperature, under the action of a magnetic field, from solution, isolate porous or hollow magnetic microsphere;
D. with porous or hollow microsphere alcohol wash clean, in porous or hollow microsphere and surfactant mass ratio 1: 1-1: 5 ratio adds the surfactant Tween-20, in porous or hollow microsphere and isopropyl alcohol mass ratio 1: 15-1: 20 ratio adds the solvent isopropyl alcohol, the ammoniacal liquor or the hydrochloric acid that add certain pH value by general consumption, add tetraethoxysilane at last, soak after 30-50 minute, extremely neutral with deionized water wash, oven dry, the superparamagnetism microballoon that obtains being coated with silicon oxide.
2. a kind of superparamagnetism method for preparing microsphere according to claim 1 is characterized in that: adopt ferric trichloride (FeCl in the steps A
36H
2O), the ferrous (FeCl of dichloride
24H
2O) and aluminum nitrate (Al (NO3)
39H
2O) preparing metal deionized water solution, the ferrous ion (Fe in the described metal ion aqueous solution
2+) and ferric ion (Fe
3+) mol ratio be 1: 2-1: 0, aluminum nitrate (Al (NO3)
39H
2O) with ferrous ion (Fe
2+), ferric ion (Fe
3+) mol ratio of both sums is 1: 0.1-1: 1.5; Perhaps by stoichiometric proportion weighing cobalt nitrate (Co (NO
3)
26H
2O), nickel nitrate (Ni (NO
3)
26H
2O), ferric nitrate (Fe (NO3)
39H
2O), wherein concentration ratio is divalent cobalt ion/bivalent nickel ion/ferric ion/hydroxide ion=1/1/2/30 (Co
2+/ Ni
2/+Fe
3+/ OH-=1/1/2/30) unit is every liter of a mole, obtain solution and mix and become metal ion solution respectively.
3. a kind of superparamagnetism method for preparing microsphere according to claim 1, it is characterized in that: the preparation method of porous or hollow microsphere is as follows among the step B:
B1) prepare polymeric dispersant under nitrogen protection, described dispersant is polyacrylic acid or polymethylacrylic acid or polyacrylamide or poly N-vinyl pyrrolidone solution, and the monomer of polymerization is a styrene, and the mass ratio of monomer and dispersant is 8: 1～12: 1;
B2) distilled water, absolute ethyl alcohol, dispersant and styrene are added in the container respectively stir, slowly be warming up to 60-80 degree centigrade, add initator azodiisobutyronitrile or dibenzoyl peroxide, isothermal reaction 15-30 hour, cooling discharging, the reactant centrifugation is also used methanol wash, obtain polymer microballoon after the drying;
B3) above-mentioned polymer microballoon is packed into filter paper bag is put into cable-styled extractor, adds dichloromethane solution, solution is heated to 40 degrees centigrade-80 degrees centigrade, linear polymer 1-4 in the extracting polymer microballoon hour, cooling obtained porous or hollow microsphere after the drying.
4. a kind of superparamagnetism method for preparing microsphere according to claim 1, it is characterized in that: add porous or hollow microsphere in the cucurbit among the described step B on Rotary Evaporators, earlier pre-exhaust, and feeding nitrogen, add metal ion solution, bleed once more and feed nitrogen, be rotated evaporation then.
5. a kind of superparamagnetism method for preparing microsphere according to claim 1 is characterized in that: among the described step D, in the ratio adding tetraethoxysilane of the mass ratio 1 of porous or hollow microsphere and tetraethoxysilane: 1-4.
6. superparamagnetism microballoon, at porous or the hollow microsphere interior polymeric ion that is magnetic, it is characterized in that: layer is coated with silicon oxide on the surface of porous or hollow microsphere.
7. a kind of superparamagnetism microballoon according to claim 6 is characterized in that: described porous or hollow microsphere adopt distilled water, absolute ethyl alcohol, dispersant and styrene polymerization to form.
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| CN109485052A (en) * | 2018-09-20 | 2019-03-19 | 四川大学 | A kind of preparation method of macropore superparamagnetism array type earth silicon material |
| CN110715538A (en) * | 2019-11-15 | 2020-01-21 | 快思瑞科技(上海)有限公司 | Expandable microsphere drying system and method |
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