CN1718619A - Magnetic composite microglobule possessing inorganic/organic core shell structure and its preparation method - Google Patents
Magnetic composite microglobule possessing inorganic/organic core shell structure and its preparation method Download PDFInfo
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- CN1718619A CN1718619A CN 200510087784 CN200510087784A CN1718619A CN 1718619 A CN1718619 A CN 1718619A CN 200510087784 CN200510087784 CN 200510087784 CN 200510087784 A CN200510087784 A CN 200510087784A CN 1718619 A CN1718619 A CN 1718619A
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Abstract
A composite magnetic microsphere with organic linorganic core-shell structure has 0.05-20 microns in diameter and high dispersity. Its controllable preparing process features that the magnetic nanoparticles are deposited on the surface of polymer core to form a magnetic shell, and features less use of chemical agents.
Description
Invention field
The present invention relates to a kind of magnetic composite microsphere and preparation method thereof, belong to the novel magnetic field of functional polymer composites with inorganic/organic core shell structure.
Background technology
The research work of magnetic composite microsphere starts from late 1970s.So-called magnetic composite microsphere, promptly be to have the powder of the nano level yardstick of the metal of magnetic or metal oxide (as Fe, Co, Ni and various forms of oxide compound thereof), carry out the compound prepared complex microsphere that goes out by certain mode with magnetic responsiveness with certain matrix micro-sphere material.
According to the difference of selected body material material, magnetic composite microsphere can have kinds such as synthetic macromolecule base magnetic microsphere, biopolymer base magnetic microsphere and inorganics magnetic microsphere.
Magnetic composite microsphere has and can suspend in liquid-phase system and can the directed characteristic that moves under extraneous the action of a magnetic field, make it at numerous areas, especially at biomedical, bioengineering field huge application potential is arranged, cause the attention and the great interest of people's height.At present, magnetic composite microsphere has represented its application prospects in these fields in the existing more research of the application of aspects such as cellular segregation, separate nucleic acid, protein purification, immobilized enzyme, immunodiagnosis, target administration and biological affinity chromatography.
Synthetic macromolecule base magnetic microsphere is paid attention to and broad research especially because of it has the excellent comprehensive performance.At present, its preparation method can be divided into following several types:
1. direct absorption method
This preparation method is with after the pre-treatment of magnetic nanoparticle process, makes it mix mutually with polymers soln, makes polymer be adsorbed on the magnetic composite microsphere that magnetic particle obtains nucleocapsid structure on every side.This method is simple, and technical requirements is very not high, and document has report more.The deficiency of this method is, gained target compound shape is often irregular, and distribution of sizes is wide, and the magnetic components content in the gained magnetic composite microsphere is low, has limited its range of application.
2. polymerization coats method
This preparation method is scattered in pretreated magnetic nanoparticle in the solution of vinyl monomer, makes fully absorption around particle such as monomer and initiator.Then, provide polymerizing condition to make monomer polymerization become the polymkeric substance shell, obtain the magnetic composite microsphere of nucleocapsid structure.
It is the preparation method of the magnetic macromolecular microsphere of shell with the amino polyacrylamide that Chinese patent bulletin CN1116353C discloses a kind of, wherein prepare the magnetic fluid that particle diameter is 7～10nm earlier, and after initiator has fully been adsorbed in the magnetic particle surface, be scattered in and contain acrylamide, allylamine or N, in the monomeric system of N '-methylene-bisacrylamide, last trigger monomer polymerization obtains target product.The open CN1375507A of Chinese patent application has described monodispersed magnetic particle has been scattered in the organic medium that contains tensio-active agent, then to wherein adding monomer, functionalized reagent, initiator, coupling agent and linking agent etc., impel monomer fully to disperse and be coated on the magnetic particle surface by stirring, the initiated polymerization that heats up afterwards obtains the core-shell structure magnetic complex microsphere of shell band functional group.
This kind technology type of polymer suitable than first method enlarged, and can introduce functional group easily in the polymkeric substance shell.The thickness of shell is also adjusted by anti-prescription of selective polymerization and technology than being easier to.But this technology is higher to technical requirements because of relating to macromolecular synthetic reaction.And the same with first method, the magnetic components content in the gained magnetic composite microsphere is low, mixes the non magnetic microballoon that homogeneous nucleation is arranged toward contact in the product, needs to separate to remove.
3. layer assembly method
The layer upon layer electrostatic self-assembling technique that with the microballoon is template is a kind of new technology for preparing the nucleocapsid structure functional microsphere.This technology is to make certain electric charge of microsphere surface band, then the polymer or the nanoparticle of oppositely charged is assembled to obtain the nucleocapsid structure microballoon by electrostatic adhesion.Document (FrankCaruso, Andrei S.Susha, Michael Giersig, Helmuth M hwald.MagneticCore-Shell Particles:Preparation of Magnetite Multilayers on PolymerLatex Microspheres.Adv.Mater., 1999,11 (11): 950-953) having reported a kind of is the layer upon layer electrostatic self-assembling method of template with the polystyrene microsphere, and preparing with the polystyrene microsphere is the magnetic composite microsphere of examining, comprise the multi-layered magnetic shell.Though this technology can be by design Fe
3O
4The number of plies of magnetic particle shell is controlled the grain size of end product, but magnetic shell thickness variable range is narrow, and the preparation section complexity.
4. magnetic particle in-situ synthesis
The hybrid structure functional microsphere refers to a kind of its function ingredients and intersperses among microballoon inside with the form of " quantum dot ".U.S. Pat 4774265 discloses a kind of method for preparing the hybrid structure magnetic composite microsphere.In the method, can be original material with the polymer microballoon of the functional group of metal ion bonding to contain on the molecular chain, in iron salt solutions, carry out dip treating and metallic cation is introduced into microballoon inside.Then, provide reaction conditions to make metallic cation form magnetic nanoparticle, thereby obtain the magnetic composite microsphere of hybrid structure in the inner original position of polymer microballoon.
Document (Jiguang Zhang, Shengqing Xu, Eugenia Kumacheva.Polymermicrogels:reactors for semiconductor, metal and magnetic nanoparticles.J.Am.Chem.Soc., 2004,126:7908-7914) introduced with polymer gel microsphere and prepare the method for magnetic composite microsphere as " reactor ", the method for its elementary tactics and U.S. Pat 4774265 is close.
It is consistent that the advantage of magnetic particle in-situ synthesis is to guarantee to introduce the concentration ratio of the magneticsubstance in each microballoon, thereby can prepare magnetic property magnetic composite microsphere relatively uniformly.Shortcoming is the high density that is difficult to realize the magnetic particle of microballoon inside, thereby is difficult to obtain having the magnetic composite microsphere of high saturation and magnetic intensity.
Summary of the invention
One of purpose of the present invention is to design a kind of novel magnetic complex microsphere with nucleocapsid structure, its nuclear is polymer microballoon, nuclear is outer to be to serve as the magnetic shell of the main controllable thickness that constitutes with magnetic oxide nanoparticle etc., and this shell combines tight (referring to Fig. 1) with nuclear.The density of magnetic composite microsphere of the present invention and magnetic property can be regulated and control easily within the specific limits.
Two of purpose of the present invention provides a kind of method for preparing magnetic composite microsphere of the present invention.
These and other purposes of the present invention, feature and advantage will become cheer and bright after the reference accompanying drawing reads following explanation.
The accompanying drawing summary
Fig. 1 is gained Fe in the embodiment of the invention 2
3O
4The transmission electron microscope photo of/polystyrene core/shell structure magnetic composite microsphere.
Detailed Description Of The Invention
Magnetic composite microsphere of the present invention is a kind of microballoon with nucleocapsid structure, and its nuclear is to be selected from polyphenyl The polymer microballoon of ethene, crosslinked polystyrene or styrene based copolymer, nuclear is outer to be with magnetic Nano Particle is the main magnetic shell that consists of.
In magnetic composite microsphere of the present invention, described polymer microballoon is that particle diameter is 0.05～20 μ m Monodisperse polymer micro-sphere in the scope.
In magnetic composite microsphere of the present invention, described magnetic nanoparticle is nanometer Fe3O
4Particle, nanometer γ-Fe2O
3The ferrite particle of particle or other nano-grade sizes and other nano-magnetic grains Son is such as cobalt particle, iron particle, nickel particles, dilval particle etc.
The preparation method of magnetic composite microsphere of the present invention comprises the steps:
1) adopt micro-emulsion polymerization, letex polymerization or diffuse-aggregate method prepare particle size range in 0.05～20 μ m monodisperse polymer micro-sphere and handle by ordinary method and to obtain the exsiccant polymer microballoon;
2) will be scattered in the vitriol oil from the exsiccant polymer microballoon of step 1), room temperature to 100 ℃ following constant temperature, under stirring action, carry out sulfonation reaction, the time of sulfonation reaction is 10 minutes～48 hours, centrifugation reaction product is then also used washings such as methyl alcohol, ethanol, propyl alcohol, butanols or acetone, and obtaining outside shell is the nucleocapsid structure polymer microballoon of sulfonation gel coat;
3) under agitation will be from step 2) polymer microballoon impregnated in the aqueous solution of salt of the aqueous solution of capacity soluble ferric iron salt or molysite and other transition metals, under nitrogen protection, flooded 3～96 hours;
4) will carry out centrifugation from the suspension of step 3), the isolated saturated microballoon that has adsorbed the soluble salt metallic cation is scattered in the deionized water again, 30～100 ℃ of following constant temperature, the NaOH aqueous solution of adding 2mol/L makes the pH of reaction system reach 8～13 under high-speed stirring, reacted 10～200 minutes, stop heating, naturally cool to room temperature, then that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere that the present invention has nucleocapsid structure.
The inventive method the 1st) step in, monodisperse polymer micro-sphere can adopt conventional micro-emulsion polymerization, letex polymerization or dispersion polymerization processes preparation, for example referring to 1. Hu Jianhua, Lv Xuliang, Yang Wuli, Xu Xiaojun, the mansion longevity is wide, " Preparation of monodisperse polymer microsphere and influence factor thereof ", Fudan University's journal (natural science edition), 1997,36 (4): 464-468; 2. yellow loyal soldier, Gao Jining, Wang Jing, Tang Fangqiong, Yuan Chunwei, " preparation of modified polystyrene and the assembling of colloidal crystal thereof ", Acta PhySico-Chimica Sinica, 2004,20 (6): 651-655; 3.Xie G, Zhang QY, Luo ZP, Wu M, Li TH, " Preparation and Characterization of Monodisperse MagneticPoly (styrene butyl acrylate methacaylic acid) Microspheres in the Presenceof a Polar Solvent ", J.Appl.Polym.Sci., 2003,87:1733-1738; 4.ZhangJH, Chen Z, Wang ZL, Zhang WY, Ming NB, " Preparation ofmonodisperse polystyrene spheres in aqueous alcohol system ", MaterialsLetters, 2003,57:4466-4470.
The inventive method the 2nd) carry out sulfonation reaction in the step from the exsiccant polymer microballoon of step 1)., will be scattered in the vitriol oil from the exsiccant polymer microballoon of step 1) for this reason, carry out sulfonation at constant temperature in room temperature to 100 ℃ with under stirring, the time of sulfonation reaction is 10 minutes～48 hours.After sulfonation reaction finishes, wash 3 times with the reaction product centrifugation and with methyl alcohol, ethanol, propyl alcohol, butanols or acetone etc., obtaining outside shell thus is the nucleocapsid structure polymer microballoon of sulfonation gel coat.The 2nd) step in, be 1: 1～1: 200 from the exsiccant polymer microballoon of step 1) and the mass ratio of the vitriol oil, preferred 1: 5～1: 100, more preferably 1: 10～1: 50.
The inventive method the 3rd) step in, under agitation use soluble ferric iron salt such as FeCl
3And/or FeCl
24H
2The salt of the aqueous solution of O or molysite and other transition metals such as CoSO
47H
2O, MnCl
24H
2The aqueous solution of O etc. is to from step 2) polymer microballoon flood, obtain suspension.Mass ratio as the aqueous solution of the salt of the soluble ferric iron salt of soaker or molysite and other transition metals is 1: 10～1: 200, preferred 1: 20～1: 100, and more preferably 1: 40～1: 80.Dipping time is 3 hours～96 hours, preferred 6 hours～72 hours, and more preferably 12 hours～48 hours.Dipping temperature in this step is unimportant usually, for example can be 5 ℃～80 ℃, and preferred 10 ℃～60 ℃, more preferably room temperature～40 ℃.
The inventive method the 4th) step in, will obtain the saturated microballoon that adsorbs the soluble salt metallic cation from the suspension centrifugation of step 3).Then this microballoon is scattered in the deionized water again, under 30～100 ℃ and high-speed stirring, adds the NaOH aqueous solution of 2mol/L, make the pH of whole reaction system reach 8～13, reacted then 10～200 minutes, stop heating, naturally cool to room temperature at constant temperature.At last that product is settlement separate, use the deionized water centrifuge washing, obtain the magnetic composite microsphere that the present invention has nucleocapsid structure.The 4th) in the step, the saturated microballoon that has adsorbed the soluble salt metallic cation is 1: 5～1: 150 with mass ratio as the deionized water of dispersion medium, preferred 1: 10～1: 100, more preferably 1: 20～1: 60.Preferably in this step, undertaken settlement separate by the external magnetic field effect.
Magnetic composite microsphere of the present invention is characterised in that the magnetic shell combines firmly with nuclear, structure is closely knit, mechanical property is good, the thickness of magnetic shell is controlled in certain range scale, thereby makes the character of magnetic composite microsphere and performance comprise that density and magnetic property etc. are also controlled in certain numerical range.The magnetic of magnetic composite microsphere of the present invention is stronger, can realize rapidly by the effect of external magnetic field separating.Its preparation method is simple, and low production cost is applicable to that styrenic with different-grain diameter as original material, has industrial value and market application foreground.
Embodiment
Be reference example of the present invention and embodiment below, be understood that these embodiment do not limit the scope of the invention.
Reference example 1
The monodisperse polystyrene microsphere for preparing diameter 500nm by dispersion polymerization
Get the 0.22g sodium lauryl sulphate and the 0.20g Potassium Persulphate is dissolved in the mixed solvent of ethanol and water.Above-mentioned solution is moved in the 250mL four-hole boiling flask, under nitrogen atmosphere and high-speed stirring, add the styrene monomer of 9mL then.In 70 ℃ water bath with thermostatic control, carried out polyreaction 8 hours.Finish reaction, with the reaction product centrifugation and with deionized water wash repeatedly, last freeze-drying is preserved standby.
Reference example 2
The monodisperse polystyrene microsphere for preparing diameter 1 μ m by dispersion polymerization
Getting the 0.143g Diisopropyl azodicarboxylate is dissolved in the 10g styrene monomer.1.0g PVP (K-30, import packing, Beijing Yili Fine Chemicals Co., Ltd.) is added in the mixed solvent of being made up of the second alcohol and water with the 0.5mL dodecanol, stirring makes its dissolving, be transferred in the four-hole boiling flask of 250mL, letting nitrogen in and deoxidizing 10 minutes, and be warming up to 60 ℃.To wherein adding the styrene monomer that has dissolved Diisopropyl azodicarboxylate, under nitrogen protection, carried out polyreaction 20 hours.Finish reaction, washing with alcohol three times are also used in the reaction product centrifugation, last freeze-drying is preserved standby.
Reference example 3
The monodisperse polystyrene microsphere for preparing diameter 250nm by seeded emulsion polymerization.
140g is contained monomeric mixture (60g vinylbenzene; 78g water and 2.0g emulsifying agent NTS (BASF Aktiengesellschaft) and 30g initiator solution (1wt% Potassium Persulphate) are added in the polystyrene seed emulsion after 12.3g (2wt%) dilution; mechanical stirring; logical nitrogen protection; in 80 ℃ of following polyreactions 2 hours, and then continued polyreactions 1 hour down in 85 ℃.After reaction is finished, make emulsion naturally cool to room temperature, remove residual monomer with nitrogen bubble.Washing with alcohol three times are also used in the reaction product centrifugation, and last freeze-drying is preserved standby.
Reference example 4
The monodisperse cross-linked polystyrene microsphere for preparing diameter 1 μ m by dispersion polymerization.
The 0.105g Potassium Persulphate is dissolved in the 10mL deionized water, gets persulfate aqueous solution.The 0.11g sodium lauryl sulphate is dissolved in the mixed solvent of being made up of 10mL water and 50mL ethanol, moves into four-hole boiling flask, magnetic agitation is at N
2Be warming up to 70 ℃ under the protection, add 4.5mL styrene monomer and 0.0612g Vinylstyrene, add above-mentioned persulfate aqueous solution at last.Reaction is 8 hours under 70 ℃ of constant temperature and magnetic stirring.Washing with alcohol three times are also used in the reaction product centrifugation, and last freeze-drying is preserved standby.
Reference example 5
The general method of sulfonating of polystyrene microsphere
1g is dropped in the round-bottomed flask of 100mL through exsiccant polystyrene microsphere (reference example 1,2,3 or 4), add the 18mL vitriol oil then, in 40 ℃ of waters bath with thermostatic control, carry out the sulfonation reaction certain hour under the magnetic agitation effect.Finish reaction, the ethanol centrifuge washing is also used in the reaction product centrifugation.
Embodiment 1
With 1g from the monodisperse polystyrene microsphere of reference example 1 by the sulfonation 4 hours in the vitriol oil of the universal method of reference example 5.At 50mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonated polystyrene microballoon 24 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, the saturation magnetization that promptly gets magnetic composite microsphere 1. these magnetic composite microspheres 1 of nucleocapsid structure is 30.97emu/g.
Embodiment 2
With 1g from the monodisperse polystyrene microsphere of reference example 1 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 50mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonation microballoon 4 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere 2 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 2 is 26.42emu/g.
Embodiment 3
With 1g from the monodisperse polystyrene microsphere of reference example 1 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 50mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonated polystyrene microballoon 12 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere 3 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 3 is 32.98emu/g.
Embodiment 4
With 1g from the monodisperse polystyrene microsphere of reference example 1 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 50mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonated polystyrene microballoon 24 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere 4 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 4 is 33.57emu/g.
Embodiment 5
With 1g from the monodisperse polystyrene microsphere of reference example 1 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 60mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonated polystyrene microballoon 48 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere 5 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 5 is 34.57emu/g.
Embodiment 6
With 1g from the monodisperse polystyrene microsphere of reference example 2 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 60mL FeCl
3With FeCl
24H
2Under agitation flooded above-mentioned sulfonated polystyrene microballoon 48 hours in the saturated aqueous solution of O, protect with nitrogen in room temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the magnetic composite microsphere 6 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 6 is 32.02emu/g.
Embodiment 7
With 1g from the monodisperse polystyrene microsphere of reference example 3 by the sulfonation 4 hours in the vitriol oil of the universal method of reference example 5.At 40ml FeCl
3With FeCl
24H
2In the saturated aqueous solution of O, under agitation flooded above-mentioned sulfonated polystyrene microballoon 48 hours, nitrogen protection in 40 ℃ of constant temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the polystyrene-based magnetic composite microsphere 7 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 7 is 31.31emu/g.
Embodiment 8
With 1g from the monodisperse polystyrene microsphere of reference example 4 by the sulfonation 8 hours in the vitriol oil of the universal method of reference example 5.At 40ml FeCl
3With FeCl
24H
2In the saturated aqueous solution of O, under agitation flooded above-mentioned sulfonated polystyrene microballoon 48 hours, nitrogen protection in 40 ℃ of constant temperature.Sulfonation microballoon centrifugation with behind the dipping is scattered in the 50mL deionized water, is container with the 100mL four-hole boiling flask, and nitrogen protection is in 65 ℃ of following constant temperature.Add the NaOH aqueous solution of 2mol/L then under high-speed stirring, make the pH of reaction system reach 12～13, constant temperature reacted 60 minutes down.Reaction finishes, and material naturally cools to room temperature.Utilize magnetic field that product is settlement separate, and use the deionized water centrifuge washing, promptly get the polystyrene-based magnetic composite microsphere 8 of nucleocapsid structure.The saturation magnetization of this magnetic composite microsphere 8 is 44.65emu/g.
Claims (10)
1. magnetic composite microsphere with nucleocapsid structure, wherein said nuclear is polymer microballoon, shell contains magnetic nano-particle.
2. magnetic composite microsphere as claimed in claim 1, wherein said polymer microballoon are that the polymer microballoon and the described magnetic nano-particle that are selected from polystyrene, crosslinked polystyrene or styrene based copolymer are nanometer Fe
3O
4Particle, nanometer γ-Fe
2O
3The ferrite particle of particle or other nano-grade sizes and other magnetic nanoparticles such as cobalt particle, iron particle, nickel particles, Rhometal particle etc.
3. magnetic composite microsphere according to claim 1, wherein the particle diameter of polymer microballoon is single and disperses and in 0.05～20 mu m range.
4. method for preparing as magnetic composite microsphere as described in the claim 1-3 may further comprise the steps:
1) adopt micro-emulsion polymerization, letex polymerization or diffuse-aggregate method prepare particle size range in 0.05～20 μ m monodisperse polymer micro-sphere and handle by ordinary method and to obtain the exsiccant polymer microballoon;
2) will be scattered in the vitriol oil from the exsiccant polymer microballoon of step 1), room temperature to 100 ℃ following constant temperature, under stirring action, carry out sulfonation reaction, the time of sulfonation reaction is 10 minutes～48 hours, centrifugation reaction product is then also used washings such as methyl alcohol, ethanol, propyl alcohol, butanols or acetone, and obtaining outside shell is the nucleocapsid structure polymer microballoon of sulfonation gel coat;
3) under agitation will be from step 2) polymer microballoon impregnated in the aqueous solution of salt of the aqueous solution of capacity soluble ferric iron salt or molysite and other transition metals, under nitrogen protection, flooded 3～96 hours;
4) will carry out centrifugation from the suspension of step 3), the isolated saturated microballoon that has adsorbed the soluble salt metallic cation is scattered in the deionized water again, 30～100 ℃ of following constant temperature, the NaOH aqueous solution of adding 2mol/L makes the pH of reaction system reach 8～13 under high-speed stirring, reacted 10～200 minutes, stop heating, naturally cool to room temperature, then that product is settlement separate, and use the deionized water centrifuge washing, promptly get magnetic composite microsphere with nucleocapsid structure.
5. method as claimed in claim 4 is wherein in step 2) described in the dry polymer microballoon and the mass ratio of the vitriol oil be 1: 1～1: 200, preferred 1: 5～1: 100, most preferably 1: 10～1: 50.
6. method as claimed in claim 4, wherein the mass ratio at the aqueous solution of the dry sulfonated polymer microballoon described in the step 3) and soluble iron salt brine solution or molysite and other transition metal salt is 1: 10～1: 200, preferred 1: 20～1: 100, most preferably 1: 40～1: 80; Dipping time is 3 hours～96 hours, preferred 6 hours～72 hours, and more preferably 12 hours～48 hours; And dipping temperature is 5 ℃～80 ℃, preferred 10 ℃～60 ℃, and more preferably room temperature～40 ℃.
7. method as claimed in claim 4, wherein in the absorption described in the step 4) microballoon of metallic cation be 1: 5～1: 150 with mass ratio as the water of dispersion medium, preferred 1: 10～1: 100, most preferably 1: 20～1: 60.
8. method as claimed in claim 4, wherein soluble ferric iron salt is FeCl
3And/or FeCl
24H
2The salt of O and transition metal is CoSO
47H
2O, MnCl
24H
2O etc.
9. method as claimed in claim 4, wherein said core-shell structure magnetic complex microsphere is the 4th) realize settlement separate by the external magnetic field effect in the step.
10. method as claimed in claim 4, wherein said magnetic composite microsphere, its shell are nanometer Fe
3O
4Particle, nanometer γ-Fe
2O
3Particle, ferrite nano particles or other magnetic nanoparticles such as cobalt particle, iron particle, nickel particles, Rhometal particle etc.
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| CN103834316A (en) * | 2012-11-26 | 2014-06-04 | 鸿富锦精密工业（深圳）有限公司 | Adhering structure, surface treatment agent and tearing method |
| CN104290479A (en) * | 2014-09-16 | 2015-01-21 | 吉林大学 | Method for achieving controllable writing of oily dye by using superhydrophilic interface as substrate in water environment |
| US9427396B2 (en) | 2008-06-27 | 2016-08-30 | Ucl Business Plc | Magnetic microbubbles, methods of preparing them and their uses |
| CN106478857A (en) * | 2016-10-14 | 2017-03-08 | 北京海岸鸿蒙标准物质技术有限责任公司 | For calibrating standard substance of airborne particle counter and preparation method thereof |
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| CN108531130A (en) * | 2018-03-03 | 2018-09-14 | 王艺霖 | A kind of preparation method of tiny balloon absorbing material |
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-
2005
- 2005-08-08 CN CNB2005100877847A patent/CN1315920C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9427396B2 (en) | 2008-06-27 | 2016-08-30 | Ucl Business Plc | Magnetic microbubbles, methods of preparing them and their uses |
| CN103834316B (en) * | 2012-11-26 | 2017-11-21 | 鸿富锦精密工业（深圳）有限公司 | Adhesive structure, surface conditioning agent and tear off method |
| CN103834316A (en) * | 2012-11-26 | 2014-06-04 | 鸿富锦精密工业（深圳）有限公司 | Adhering structure, surface treatment agent and tearing method |
| CN103134926A (en) * | 2013-02-27 | 2013-06-05 | 上海交通大学 | Magnetic microsphere carrier and its making method |
| CN103588919A (en) * | 2013-10-31 | 2014-02-19 | 江苏大学 | Preparation method of magnetic porous adsorbent by suspension polymerization |
| CN104290479A (en) * | 2014-09-16 | 2015-01-21 | 吉林大学 | Method for achieving controllable writing of oily dye by using superhydrophilic interface as substrate in water environment |
| CN107583574A (en) * | 2016-07-06 | 2018-01-16 | 南京理工大学 | A kind of magnetic polymer microsphere of morphology controllable and preparation method thereof |
| CN106478857A (en) * | 2016-10-14 | 2017-03-08 | 北京海岸鸿蒙标准物质技术有限责任公司 | For calibrating standard substance of airborne particle counter and preparation method thereof |
| CN108531130A (en) * | 2018-03-03 | 2018-09-14 | 王艺霖 | A kind of preparation method of tiny balloon absorbing material |
| CN110935405A (en) * | 2019-11-11 | 2020-03-31 | 湖北新纵科病毒疾病工程技术有限公司 | Preparation method of magnetic polystyrene microspheres with surfaces rich in double bonds |
| CN110935405B (en) * | 2019-11-11 | 2022-04-12 | 湖北新纵科病毒疾病工程技术有限公司 | Preparation method of magnetic polystyrene microspheres with surfaces rich in double bonds |
| CN112635143A (en) * | 2020-12-02 | 2021-04-09 | 苏州海狸生物医学工程有限公司 | Micron-sized uniform-particle biomagnetic microspheres and preparation method thereof |
| CN112807744A (en) * | 2021-01-18 | 2021-05-18 | 南京工业大学 | Magnetic dispersion solid phase extraction material for enriching pesticide and veterinary drug residues and preparation method thereof |
| CN115845816A (en) * | 2022-12-07 | 2023-03-28 | 中元汇吉生物技术股份有限公司 | Magnetic microsphere, preparation thereof and application thereof in mass spectrum sample desalting |
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