CN101328273A - Water dispersible magnetic high polymer microsphere and preparation thereof - Google Patents
Water dispersible magnetic high polymer microsphere and preparation thereof Download PDFInfo
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- CN101328273A CN101328273A CNA2008100297046A CN200810029704A CN101328273A CN 101328273 A CN101328273 A CN 101328273A CN A2008100297046 A CNA2008100297046 A CN A2008100297046A CN 200810029704 A CN200810029704 A CN 200810029704A CN 101328273 A CN101328273 A CN 101328273A
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Abstract
The invention discloses a water dispersion magnetic polymer microsphere and a preparation method thereof. Firstly, a core is prepared by soap-free emulsion polymerization, then atom transfer radical polymerization (ATRP) is utilized to actively polymerize and prepare a hydrophilic shell, and the obtained water dispersion magnetic polymer microsphere is a composite consisting of a superparamagnetic center and a high molecular polymer; an outer layer is a hydrophilic or water-soluble polymer and is prepared through an active polymerization ATRP reaction; an inner layer is a polymer which can produce an even cavity, can load a magnetic center and has good cross-linking fixation, and is generated through the soap-free emulsion polymerization; the superparamagnetic center is formed by the even cavity of the inner layer loaded with an inorganic superparamagnetic material; and the diameter range of the microsphere is between 100 and 2000nm, the magnetic content is between 3 and 50 percent, and the saturated magnetization strength is between 3.0 and 70.0emu/g. The preparation method is simple, and the produced water dispersion magnetic polymer microsphere has a controllable structure, even distribution, regular shape, adjustable magnetic content, and good biocompatibility.
Description
Technical field
The present invention relates to functional high polymer material field, particularly a kind of water dispersible magnetic high polymer microsphere and preparation method thereof.
Background technology
Magnetic macromolecular microsphere has the magnetic responsiveness of high molecular numerous characteristic and magnetic substance concurrently, is widely used in the fields such as solid phase carrier, affinity chromatography, biomedicine, cytobiology and biotechnology of magnetic plastics, magnetic rubber, organic synthesis.The structure of magnetic macromolecular microsphere generally has three kinds: (one) forms nuclear by magnetic metal oxide (as oxide compounds such as iron, cobalt, nickel), and macromolecular material is formed shell; (2) macromolecular material is as nuclear, and magneticsubstance is as shell; (3) a kind of sandwich structure, ectonexine are macromolecular material, and the middle layer is a magneticsubstance.The preparation method of magnetic macromolecular microsphere mainly comprises entrapping method and monomer polymerization method: (1) entrapping method is that magnetic particle is scattered in the macromolecular solution, makes magnetic macromolecular microsphere by methods such as atomizing, flocculation, deposition, evaporations; But, the magnetic macromolecular microsphere size distribution broad of this method preparation, out-of-shape, size is difficult to control, and magnetic content is inhomogeneous, and the strong and weak difference of microballoon magnetic is very big, polymer embedded magnetic center is incomplete, and the magnetic core easily contacts with extraneous, and magnetic is revealed easily.(2) monomer polymerization method is in the presence of magnetic particle and monomer, adds the core-shell type magnetic macromolecular microsphere that initiator, stablizer etc. are polymerized; Polymerization process mainly contains: suspension polymerization, dispersion polymerization, letex polymerization etc.; But the microballoon magnetic content of this method preparation is lower, is separated easily in the polymerization process, causes synthetic microballoon magnetic content distribution heterogeneity, and its chemistry and mechanical stability are also relatively poor.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of controllable structure is provided, is evenly distributed, regular shape, magnetic content is adjustable, the water dispersible magnetic high polymer microsphere of good biocompatibility.
Another object of the present invention is to provide a kind of preparation method of above-mentioned water dispersible magnetic high polymer microsphere.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of water dispersible magnetic high polymer microsphere is to utilize atom transfer radical polymerization (ATRP) preparation wetting ability shell again by emulsifier-free emulsion polymerization preparation nuclear earlier, comprises the steps:
(1) emulsifier-free emulsion polymerization prepares microballoon nuclear and forms living polymerization initiation center:
At first initiator and solvent are added in the reaction vessel, under atmosphere of inert gases, add the mixed solution of mix monomer and linking agent, reacted 0.5～12 hour; Slowly drip then and contain the monomer that the ATRP living polymerization causes the center, form the initiating activity center, continue reaction 6～24 hours on the surface of nuclear;
(2) microsphere surface causes the hydrophilic monomer polymerization by the ATRP living polymerization and forms shell:
Add ATRP catalyst for reaction and hydrophilic monomer in the reaction system of step 1, wherein the mol ratio in catalyzer and active centre is 1: 1, and the mol ratio in hydrophilic monomer and active centre is 20～200: 1; The amount of substance in active centre equates with the slow monomeric amount of substance that contains ATRP living polymerization initiation center that drips described in the step 1; Logical rare gas element bubbling 1～5 hour adds the aglucon of deoxygenation, and 60～100 ℃ of following stirring reactions 1～48 hour, cooling was with air bubbling termination reaction;
(3) preparation of magnetic microsphere:
Product dialysis with step 2 obtains disperses with methylene dichloride then; Add trifluoroacetic acid again, described methylene dichloride: the volume ratio of trifluoroacetic acid is 1～10: 1, stirs 1～12 hour, and hydrolysis is removed the tertiary butyl in the cross-linking products and formed even cavity; Dialysis again is then with dialyzate and ferrous ion (Fe
2+) solution is with volume ratio 1: 1～3 mixing, sealing was stirred after 12～24 hours in the inert atmosphere, and impurity is removed in dialysis again; Regulating the pH value with alkali then is 7～9, makes and carboxyl bonded ferrous iron precipitation, adds hydrogen peroxide (H again
2O
2) be ferric iron forming the superparamagnetism center with oxidation of divalent, and make magnetic center growth 4～10 hours, separate with strong magnet again, obtain water dispersible magnetic high polymer microsphere.
In the step 1, described initiator is a persulfide, preferred Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Temperature of reaction is 50～90 ℃.The consumption of initiator is 0.5%～5% of a monomer total mass; Described monomer total mass is a mix monomer quality and the monomer mass sum that contains ATRP living polymerization initiation center in the step 1.
In the step 1, described solvent is a water, consumption be in the step 1 the whole reaction system total mass 90%～99%.
In the step 1, described mix monomer is the mixture of monomer A, monomers B and monomer C; Monomer A: monomers B: the mass ratio of monomer C is 1: 0.6～5: 0.1～10; Described monomer A is an olefin(e) acid tert-butyl ester monomer, preferred tert-butyl acrylate; Described monomers B is to contain the monomer that the ATRP living polymerization causes the center, preferred vinylformic acid-3-bromopropyl alcohol ester or vinylformic acid-3-propylene chlorohydrin ester or its mixture; Described monomer C is the monomer that is used to regulate the particle performance, specifically can be fragrant alkene class such as vinylbenzene, one or more mixtures in ester class such as methyl methacrylate, methyl acrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, tert-butyl acrylate, Isooctyl acrylate monomer, Isooctyl methacrylate or the vinyl-acetic ester.
In the step 1, described linking agent is Vinylstyrene (DVB), Ethylene glycol dimethacrylate (EGDMA), N, N '-methylene-bisacrylamide (NAPP) or diacetone-acryloamide(DAA) (DAAM), the consumption of linking agent is 0.5%～7% of a described mix monomer quality.
In the step 1, the monomer that described slow dropping contains ATRP living polymerization initiation center is the monomer that contains the halogen family element, and consumption is identical with the consumption of monomers B in the mix monomer; Preferred vinylformic acid-3-bromopropyl alcohol ester, vinylformic acid-3-propylene chlorohydrin ester, methacrylic acid-3-bromopropyl alcohol ester, methacrylic acid-3-propylene chlorohydrin ester, vinylformic acid-ethylene bromohyrin ester, methacrylic acid ethylene chlorhydrin ester, vinylformic acid-ethylene chlorhydrin ester, methacrylic acid-ethylene chlorhydrin ester, 2 bromopropionic acid vinylformic acid ethylene glycol diester, 2-chloropropionic acid vinylformic acid ethylene glycol diester, 2 bromopropionic acid vinylformic acid Diethylene Glycol diester, 2-chloropropionic acid vinylformic acid Diethylene Glycol diester, 2-chloropropionic acid vinylformic acid triethylene glycol diester, 2 bromopropionic acid vinylformic acid triethylene glycol diester, one or more mixtures in 2-chloropropionic acid vinylformic acid TEG diester or the 2 bromopropionic acid vinylformic acid TEG diester; The monomeric dropping time that the described ATRP of containing living polymerization causes the center is 0.5～4 hour.
In the step 2, described catalyzer is the halogen of IB family or VIIIB family, preferred cuprous chloride, cuprous bromide, cuprous acetate, protobromide nickel, iron protochloride or palladium diacetate.
In the step 2, described hydrophilic monomer is meant to have water-soluble or wetting ability, the small-molecule substance and the polyoxyethylene acrylic ester high molecular type polymkeric substance that contain hydrophilic functional groups (as hydroxyl, amino or sulfonic group), as acrylamide (AM), Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), 2-acrylamido-2-methyl propane sulfonic acid (AMPS), vinylformic acid-2,3-dihydroxyl propyl ester (DHPA) or polyoxyethylene glycol (200,400,550,1900,5000,10000 etc.) the monomethyl ether acrylate etc.
Described aglucon is the polyamines class, preferred PMDETA (PMDETA), three-(N, N dimethylamine base ethyl) amine (Me
6TREN), second bipyridine (bpy), Tetramethyl Ethylene Diamine (TMEDA) or 1,1,4,7,10,10 '-hexamethyl Triethylenetetramine (TETA) (HMETETA).
In the step 3, it is 12000～200000 that the dialysis tubing that described dialysis is adopted allows to see through maximum molecular weight.
In the step 3, described ferrous ion (Fe
2+) solvent is iron protochloride, ferrous sulfate, ferrous phosphate or Iron diacetate.
The water dispersible magnetic high polymer microsphere that adopts method for preparing to obtain is by superparamagnetism center and the common mixture of forming of high molecular polymer; Skin is wetting ability or water-soluble polymers, obtains by living polymerization ATRP reaction; Internal layer generates by emulsifier-free emulsion polymerization for can produce even cavity and can load the crosslinked polymkeric substance that fixes in magnetic center; Load inorganic superparamagnetic material with the even cavity of internal layer and form the superparamagnetism center; Described diameter of micro ball scope is 100～2000nm, and magnetic content is 3～50%, and saturation magnetization is 3.0～70.0emu/g.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts emulsifier-free emulsion polymerization and ATRP living polymerization method to combine, and has improved the polymerization efficiency of function monomer, the diameter of microsphere particles and the solid content of emulsion; The microsphere particles size distribution is even, regular shape.
(2) particle diameter of monodisperse polymer micro-sphere and size distribution are constant in magnetic history, and the magnetic macromolecular microsphere of final gained has good monodispersity; Microballoon is pure, does not have non-specific cohesion impurity; Use the skin of hydrophilic polymer, make microballoon have good water dispersible and biocompatibility as particle.
(3) inorganic particles with superparamagnetism is evenly dispersed in the whole polymer microballoon, and each microballoon contains the magnetic particle of same concentrations, thereby guarantees that all magnetic microspheres have consistent magnetic responsiveness under magnetic field; The densification or the porous magnetic polymer microsphere that can prepare various size and different magnetic content by adjustment monomeric species and feed ratio.
(4) microballoon of the present invention's preparation has good redispersibility in water, after the microballoon drying, can at an easy rate it be scattered in again in the water and stable existence, is very easy to store and transportation and preservation.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) emulsifier-free emulsion polymerization prepares microballoon nuclear and forms living polymerization initiation center
With 0.023g Potassium Persulphate (KPS, the monomer total mass 0.5%) be dissolved in the 95.5ml water, join in the four neck flasks, behind the logical N2 gas 10min, put into the oil bath that mixes up 83 ℃ of temperature, after treating that 80 ℃ of system temperatures are stablized, drip styrene (1.73g), tert-butyl acrylate (1.73g), the mixed solution of 2-chloropropionic acid vinylformic acid ethylene glycol diester (0.52g) and linking agent EGDMA 0.023g, behind the reaction 40min, (0.52g, holding temperature continue stirring reaction 8h to drip 2-chloropropionic acid vinylformic acid ethylene glycol diester, stop heating, naturally cool to room temperature under stirring.Centrifugal 15min, rotating speed is 3000r/min, gets emulsion after the separation.Surveying its solid content is 4.1%; It is 520nm that scanning electron microscope (SEM) records average particle diameter.
(2) microsphere surface causes the hydrophilic monomer polymerization by the ATRP living polymerization and forms shell
Get above-mentioned emulsion 20ml and (contain the about 0.82g of emulsion particle, it is active centre 0.50mmol that the surface contains initiator 2-chloropropionic acid vinylformic acid ethylene glycol diester), adding 5.69g is 49mmol Hydroxyethyl acrylate (HEA), 0.05g be 0.50mmol catalyzer cuprous chloride (CuCl), behind argon gas (Ar) bubbling 1h, the aglucon PMDETA 0.092g 0.50mmol that adds bubbling deoxygenation, behind reaction 18h under 75 ℃, cooling, open stopper drum air termination reaction, the dialysis repeatedly of reaction solution water obtains the dialysis emulsion.Surveying its solid content is 15.1%; It is 1050nm that scanning electron microscope (SEM) records average particle diameter.。
(3) preparation of magnetic microsphere
The 15ml emulsion of (2) preparation is extremely anhydrous with the methyl alcohol dialysis, after volatilizing solvent seasoning fully, obtain the 2.84g white solid, methylene dichloride and 6.7ml trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse the gained solid with 20ml, stir 12h and remove the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 27ml, again with the FeCl of dialyzate and 5Wt%
2Solution 27ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, it is 8 to make and carboxyl bonded ferrous iron precipitates that the sodium hydroxide solution that adds 2Wt% is regulated pH value, adds 10mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or Y-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 5 times, obtained water dispersible magnetic high polymer microsphere 2.65g.The mean diameter of gained magnetic macromolecular microsphere is 1050nm, and magnetic content is 5.7%, and saturation magnetization is 12.2emu/g.
Embodiment 2
(1) emulsifier-free emulsion polymerization prepares microballoon nuclear and forms living polymerization initiation center
0.045g Potassium Persulphate (KPS, monomer total mass 1%) is dissolved in the 95.5ml water, joins in the four neck flasks, logical N
2Behind the gas 10min, put into the oil bath that mixes up 83 ℃ of temperature, after treating that 80 ℃ of system temperatures are stablized, the mix monomer 5min of drip styrene 1.73g, tert-butyl acrylate 1.73g, 2-chloropropionic acid vinylformic acid ethylene glycol diester 0.52g and linking agent EGDMA 0.068g (monomer total mass 1.5%) behind the reaction 40min, drips 2-chloropropionic acid vinylformic acid ethylene glycol diester 0.52g, holding temperature, continue stirring reaction 8h, stop heating, naturally cool to room temperature under stirring.Centrifugal 15min, rotating speed is 3000r/min, gets emulsion after the separation.Surveying its solid content is 4.2%; It is 500nm that scanning electron microscope (SEM) records average particle diameter.
(2) microsphere surface causes the hydrophilic monomer polymerization by the ATRP living polymerization and forms shell
Get above-mentioned emulsion 20ml, (contain the about 0.84g of emulsion particle, the surface contains the about 0.1g 0.5mmol of initiator 2-chloropropionic acid vinylformic acid ethylene glycol diester) add 11.38g 98mmol Hydroxyethyl acrylate (HEA), 0.05g 0.5mmol catalyzer cuprous chloride (CuCl) is behind argon gas (Ar) bubbling 1h, the aglucon PMDETA 0.092g 0.5mmol that adds bubbling deoxygenation, behind reaction 18h under 75 ℃, cooling, drum air termination reaction, the dialysis repeatedly of reaction solution water obtains the dialysis emulsion.Surveying its solid content is 21.3%; It is 1650nm that scanning electron microscope (SEM) records average particle diameter.。
(3) preparation of magnetic microsphere
The 15ml emulsion of (2) preparation is extremely anhydrous with the methyl alcohol dialysis, after volatilizing solvent seasoning fully, obtain the 4.88g white solid, methylene dichloride and 6.7ml trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 1: 1) disperse the gained solid with 20ml, stir 6h and remove the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 27ml, again with the FeCl of dialyzate and 5Wt%
2Solution 27ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, it is 8 to make and carboxyl bonded ferrous iron precipitates that the sodium hydroxide solution that adds 2Wt% is regulated pH value, adds 10mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or Y-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 5 times, obtained water dispersible magnetic high polymer microsphere 4.56g.The diameter of gained magnetic macromolecular microsphere is 1650nm, and magnetic content is 3.2%, and saturation magnetization is 4.9emu/g.
Embodiment 3
(1) emulsifier-free emulsion polymerization prepares microballoon nuclear and forms living polymerization initiation center
0.09g (monomer total mass 2%) Potassium Persulphate is dissolved in the 90.7ml water, join in the four neck flasks, behind the logical N2 gas 10min, put into the oil bath that mixes up 83 ℃ of temperature, after treating that 80 ℃ of system temperatures are stablized, drip styrene 3.46g, tert-butyl acrylate 3.46g, the mix monomer 5min of 2-chloropropionic acid vinylformic acid ethylene glycol diester 1.04g and linking agent EGDMA 0.312g (monomer total mass 3.5%), behind the reaction 40min, drip 2-chloropropionic acid vinylformic acid ethylene glycol diester 1.04g, holding temperature, continue stirring reaction 8h, stop heating, naturally cool to room temperature under stirring.Centrifugal 15min, rotating speed is 3000r/min, gets emulsion after the separation.Surveying its solid content is 8.7%; It is 1040nm that scanning electron microscope (SEM) records average particle diameter.
(2) microsphere surface causes the hydrophilic monomer polymerization by the ATRP living polymerization and forms shell
Get above-mentioned emulsion 20ml, (contain the about 1.74g of emulsion particle, the surface contains the about 0.2g 0.98mmol of initiator 2-chloropropionic acid vinylformic acid ethylene glycol diester) add 5.69g 49mmol Hydroxyethyl acrylate (HEA), 0.10g 0.98mmol catalyzer cuprous chloride (CuCl) is behind argon gas (Ar) bubbling 1h, the aglucon PMDETA 0.184g 0.98mmol that adds bubbling deoxygenation, behind reaction 18h under 75 ℃, cooling, drum air termination reaction, the dialysis repeatedly of reaction solution water obtains the dialysis emulsion.Surveying its solid content is 13.6%; It is 1500nm that scanning electron microscope (SEM) records average particle diameter.
(3) preparation of magnetic microsphere
The 15ml emulsion of (2) preparation is extremely anhydrous with the methyl alcohol dialysis, after volatilizing solvent seasoning fully, obtain the 2.04g white solid, methylene dichloride and 5ml trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 10: 1) disperse the gained solid with 15ml, stir 6h and remove the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 20ml, again with the FeCl of dialyzate and 5Wt%
2Solution 20ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 9, makes and carboxyl bonded ferrous iron precipitation, adds 8mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or Y-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.98g.The diameter of gained magnetic macromolecular microsphere is 1500nm, and magnetic content is 30.0%, and saturation magnetization is 42.2emu/g.
Embodiment 4～9 related conditional parameters see Table 1, and other steps are with embodiment 1
Each specific embodiment of table 1
Claims (8)
1, a kind of preparation method of water dispersible magnetic high polymer microsphere is characterized in that comprising the steps:
(1) emulsifier-free emulsion polymerization prepares microballoon nuclear and forms living polymerization initiation center:
At first initiator and solvent are added in the reaction vessel, under atmosphere of inert gases, add the mixed solution of mix monomer and linking agent, reacted 0.5～12 hour; Slowly drip then and contain the monomer that the ATRP living polymerization causes the center, form the initiating activity center, continue reaction 6～24 hours on the surface of nuclear;
(2) microsphere surface causes the hydrophilic monomer polymerization by the ATRP living polymerization and forms shell:
Add ATRP catalyst for reaction and hydrophilic monomer in the reaction system of step 1, wherein the mol ratio in catalyzer and active centre is 1: 1, and the mol ratio in hydrophilic monomer and active centre is 20～200: 1; The amount of substance in active centre equates with the slow monomeric amount of substance that contains ATRP living polymerization initiation center that drips described in the step 1; Logical rare gas element bubbling 1～5 hour adds the aglucon of deoxygenation, and 60～100 ℃ of following stirring reactions 1～48 hour, cooling was with air bubbling termination reaction;
(3) preparation of magnetic microsphere:
Product dialysis with step 2 obtains disperses with methylene dichloride then; Add trifluoroacetic acid again, described methylene dichloride: the volume ratio of trifluoroacetic acid is 1～10: 1, stirs 1～12 hour, and hydrolysis is removed the tertiary butyl in the cross-linking products and formed even cavity; Dialysis again mixes with ferrous ion solution dialyzate then with volume ratio 1: 1～3, sealing was stirred after 12～24 hours in the inert atmosphere, and impurity is removed in dialysis again; Regulating the pH value with alkali then is 7～9, make and carboxyl bonded ferrous iron precipitation, adding hydrogen peroxide again is ferric iron forming the superparamagnetism center with oxidation of divalent, and makes magnetic center growth 4～10 hours, separate with strong magnet again, obtain water dispersible magnetic high polymer microsphere.
2, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: in the step 1, described initiator is a persulfide; The consumption of initiator is 0.5%～5% of a monomer total mass; Described monomer total mass is a mix monomer quality and the monomer mass sum that contains ATRP living polymerization initiation center in the step 1.
3, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: in the step 1, described mix monomer is the mixture of monomer A, monomers B and monomer C; Monomer A: monomers B: the mass ratio of monomer C is 1: 0.6～5: 0.1～10; Described monomer A is an olefin(e) acid tert-butyl ester monomer, and described monomers B is to contain the monomer that the ATRP living polymerization causes the center; Described monomer C is the monomer that is used to regulate the particle performance.
4, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1, it is characterized in that: in the step 1, described linking agent is Vinylstyrene, Ethylene glycol dimethacrylate, N, N '-methylene-bisacrylamide or diacetone-acryloamide(DAA), the consumption of linking agent are 0.5%～7% of described mix monomer quality.
5, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1, it is characterized in that: in the step 1, the monomer that described slow dropping contains ATRP living polymerization initiation center is the monomer that contains the halogen family element, and consumption is identical with the consumption of monomers B in the mix monomer.
6, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: in the step 2, described catalyzer is the halogen of IB family or VIIIB family.
7, the preparation method of water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: in the step 2, described hydrophilic monomer is small-molecule substance and the polyoxyethylene acrylic ester high molecular type polymkeric substance that contains hydrophilic functional groups.
8, a kind of water dispersible magnetic high polymer microsphere is characterized in that: adopt each described method of claim 1-7 to be prepared into, by superparamagnetism center and the common mixture of forming of high molecular polymer; Skin is wetting ability or water-soluble polymers, obtains by living polymerization ATRP reaction; Internal layer generates by emulsifier-free emulsion polymerization for can produce even cavity and can load the crosslinked polymkeric substance that fixes in magnetic center; Load inorganic superparamagnetic material with the even cavity of internal layer and form the superparamagnetism center; Described diameter of micro ball scope is 100～2000nm, and magnetic content is 3～50%, and saturation magnetization is 3.0～70.0emu/g.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817960A (en) * | 2010-03-17 | 2010-09-01 | 中国石油大学(华东) | Method for preparing magnetic composite nanoparticles with core-shell structure |
| CN101559343B (en) * | 2009-04-16 | 2011-06-22 | 同济大学 | Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique |
| CN104804127A (en) * | 2015-05-13 | 2015-07-29 | 北京中科紫鑫科技有限责任公司 | Preparing method of magnetic microspheres |
| CN104892827A (en) * | 2015-05-13 | 2015-09-09 | 北京中科紫鑫科技有限责任公司 | Method used for preparing magnetic composite microspheres |
| CN114609271A (en) * | 2022-02-22 | 2022-06-10 | 北京化工大学 | Method for simultaneously detecting 3-chloropropanol ester and glycidyl ester in vegetable oil based on magnetic solid-phase extraction |
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2008
- 2008-07-23 CN CNA2008100297046A patent/CN101328273A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559343B (en) * | 2009-04-16 | 2011-06-22 | 同济大学 | Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique |
| CN101817960A (en) * | 2010-03-17 | 2010-09-01 | 中国石油大学(华东) | Method for preparing magnetic composite nanoparticles with core-shell structure |
| CN104804127A (en) * | 2015-05-13 | 2015-07-29 | 北京中科紫鑫科技有限责任公司 | Preparing method of magnetic microspheres |
| CN104892827A (en) * | 2015-05-13 | 2015-09-09 | 北京中科紫鑫科技有限责任公司 | Method used for preparing magnetic composite microspheres |
| CN104892827B (en) * | 2015-05-13 | 2016-06-08 | 北京中科紫鑫科技有限责任公司 | A kind of method preparing magnetic composite microsphere |
| CN104804127B (en) * | 2015-05-13 | 2016-06-08 | 北京中科紫鑫科技有限责任公司 | The preparation method of a kind of magnetic microsphere |
| CN114609271A (en) * | 2022-02-22 | 2022-06-10 | 北京化工大学 | Method for simultaneously detecting 3-chloropropanol ester and glycidyl ester in vegetable oil based on magnetic solid-phase extraction |
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