CN1122674C - nm Microsphere of magnetic polymer and its preparing process - Google Patents
nm Microsphere of magnetic polymer and its preparing process Download PDFInfo
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- CN1122674C CN1122674C CN 01126182 CN01126182A CN1122674C CN 1122674 C CN1122674 C CN 1122674C CN 01126182 CN01126182 CN 01126182 CN 01126182 A CN01126182 A CN 01126182A CN 1122674 C CN1122674 C CN 1122674C
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Abstract
The present invention relates to a nanometer microsphere of magnetic polymers and a preparation method thereof. Firstly, an inorganic nanometer iron oxide microsphere with superparamagnetism is synthesized by using a chemical precipitation method; secondly, through using a polymerization method of inverse microemulsion, hydrophilic monomers, such as acrylamide, acrylics, etc. react in an oxidation-reduction or thermal initiation system in which an emulsifying agent, an initiator, a crosslinking agent and the iron oxide microsphere are added; reaction is controlled in certain material feeding range so as to synthesize a magnetic polymer microsphere with superparamagnetism and a particle diameter of 70 to 140 nm under mild reaction condition. The particle diameter of a swollen microsphere formed by a phase inversion method is from 80 to 250mm. The present invention has the advantages of simple method, easy acquirement of raw materials, controllable particle diameter of the microsphere, etc.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to polymer nano-microspheres that has superparamagnetism and preparation method thereof.
Technical background
Polymer microsphere has the advantage of many uniquenesses: specific surface area is big; Microspherulite diameter size all-and may command; The polymkeric substance wide material sources comprise natural and synthetic macromolecule; Can select various copolymerization function monomers and polymerization technique, carry out polymer microsphere design etc.Therefore, the polymer microsphere of functionalization can be widely used in many fields, carries medical latex reagent, biomolecular labeling and spike etc. as the medicine of biological chemistry and biomedical aspect is directed.High-performance polymer coating and printing ink, organic and inorganic matrix material, micro encapsulation, polymer microporous material, catalysis, absorption and carrier of separating (as chromatographic column filler), and as the tip materials of purposes such as information industry and microelectronics industry, the research of this direction become in recent years at material, Chemistry and Physics of Polymers, the proposition of the forward position of interdisciplinary fields such as biology and life subject, biology, medical science, pharmacy, etc. the field be with a wide range of applications.
The research of magnetic macromolecular microsphere starts from the seventies, and it removes has the characteristic of high molecular particle, can give its multiple reactive functional group in surface by copolymerization, surface modification, (as: OH ,-COOH ,-COH ,-NH
2Deng), also because of having magnetic, can under the effect of externally-applied magnetic field, separate easily, there is the scholar that it is called power particle (dynabead) visually abroad.Magnetic macromolecular microsphere with superparamagnetism has a wide range of applications in biomedical (clinical diagnosis, enzyme mark, targeted drug), cytology (cell marking, cellular segregation etc.) and biotechnology fields such as (immobilizations of enzyme) as novel functional high molecule material.Promptly when externally-applied magnetic field dropped to zero, magnetic polymer microsphere did not almost have remanent magnetism to stay to so-called superparamagnetism (superparamagnetic).
From the situation of present research, magnetic macromolecular microsphere is generally nuclear/shell-type structure: form nuclear by metal oxide (as oxide compounds such as iron, cobalt, nickel), macromolecular material is formed shell; Perhaps with macromolecular material as nuclear, magneticsubstance is as shell; In addition, also can make sandwich structure, promptly outer, internal layer is a macromolecular material, and the middle layer is a magneticsubstance.
Daniel is with Fe
3O
4(d=0.01 μ m) handles with hydrocarbon ils, carries out letex polymerization in the presence of emulsifying agent, initiator, obtains the polystyrene magnetic microsphere (Daniel J C, Schubbiser J L, USP4,358,388,1982) of particle diameter less than 1 μ m; Iman is the same St of magnetic grain, DVB, the BPO supersound process of particle diameter 20 μ m, with improved suspension polymerization polymerization obtain 104～295 μ m magnetic microsphere (Iman M, celebbiss, ozdural A R, Reactive Polym., 1992,17:325); Usefulness magnetic fluids such as Sun Zonghua are examined as magnetic, adopt improved emulsion polymerization and dispersion copolymerization method, synthesize to obtain particle size range respectively at the polystyrene microsphere of 0.06～10 μ m and 100～1000 μ m, and simultaneously, its seminar directly utilizes Fe
3O
4Magnetic is examined as magnetic, adds PEG and carries out supersound process, adopts dispersion copolymerization method, makes 50-600 μ m and is evenly distributed, polystyrene microsphere (Qiu Guangming, Sun Zonghua, chemical reagent, 1993,15 (4): 324) that magneticinduction is strong; Furusawa deposits to the magnetic grain on the polymer latex particle of band functional group, then, uses the seeding polymerization method again, obtains the magnetic microsphere of sandwich type structural.The kind of initiator and the consumption of emulsifying agent are system agglutinative important factors.Electronic Speculum result's demonstration, and the surface of magnetic polymer microsphere and unfairness (Ugelstad J, Mork P C, Schmid R, et al, Polym Int, 1993,30:157.).
The research group of Ugelstad is in single dispersion, the direct compound of precipitated iron in the expanded polystyrene microballoon.When PH and temperature rising, the ferriferous oxide of making has superparamagnetism (Superparamagnetic), the micron-sized magnetic polymer microsphere of successful preparation, and be used for biomedicine field (Furusawa K, Nagashima K, Anzai C, Colloid Polym Sci, 1994,272:1104.).
Elaissari etc. are nuclear absorption magnetic Fe with the synthetic PS of soap-free polymerization
3O
4Particle, polymerization NIPAM is a shell then, the magnetic polymer microsphere of the nucleocapsid structure of synthetic monodispersed submicron (200-400nm) (Sauzedde F, ElaissariA, Pichot C, Colloid Polym Sci, 1999,277:846.).
More than in Zhi Bei the method, all be divided into for two steps at least: the first step is the synthesizing magnetic inorganic particles, and second step added polymerization system polymerization formation magnetic macromolecular microsphere with the magnetic inorganic particulate then.Preparation technology's more complicated.
The preparation method of above magnetic polymer microsphere can only Synthetic 2 00nm even micron-sized magnetic polymer microsphere, does not see the pertinent literature report of particle diameter less than the magnetic polymer microsphere of 100nm so far.And mostly adopt the system of oil-soluble polymers microballoon among the preparation method.
Summary of the invention
The objective of the invention is to propose a kind of superparamagnetism that has, particle diameter is being nano level hydrophilic magnetic polymer nano-microspheres and preparation method thereof.
The magnetic polymer microsphere that the present invention proposes, be that the polymkeric substance that produces with hydrophilic monomer polymerizations such as acrylic amide and acrylic acid or the like is an integument, with the inorganic magnetic material ferriferous oxide is the polymer microballoon of nuclear, earlier by the synthetic ferriferous oxide inorganic microspheres of solution deposit, use conversed phase micro emulsion copolymerization method synthesizing magnetic polymer microballoon again, its particle diameter is between the 70-140 nanometer, and magnetic saturation intensity is 1.0-15.0emu/g, and has superparamagnetism.Can with the phase reversion method with this magnetic polymer microsphere swelling in water, particle diameter is between the 80-250 nanometer.Because the particle diameter yardstick of microballoon is a nano level, so claim that this microballoon is the polymer nano-microspheres with superparamagnetism.
The polymkeric substance integument of above-mentioned microballoon can be a homopolymer, also can be multipolymer.Used hydrophilic monomer can be that acrylamide (AM), vinylformic acid (AA), methacrylic acid (MAA), vinylformic acid are received (NaAA), toxilic acid (MA), methylene-succinic acid (IA) etc. one or more.
The nuclear ferriferous oxide of above-mentioned microballoon is divalent iron salt and trivalent iron salt.
The above-mentioned magnetic polymer microsphere that the present invention proposes by the synthetic ferriferous oxide inorganic microspheres of solution deposit, is polymerized by the conversed phase micro emulsion copolymerization method earlier again, and its concrete preparation process is as follows:
1. solution deposit synthesizes the ferriferous oxide inorganic microspheres: two valency molysite and trivalent iron salt are dissolved in an amount of water, and the mol ratio of two valency molysite and trivalent iron salt is 0.5-5.0, and logical nitrogen drives oxygen, 10-100 minute.Alkaline solution dropwise adds under mechanical stirring in the iron salt solutions slowly, and temperature remains on 15-30 ℃.After dripping end, continue stirring and also be warming up to 70-95 ℃ of heating 0.5-3.0 hour.Keep the nitrogen oxygen-free environment in the adition process always.After heating finished, product was collected with magnetic field separation, and was dispersed in again in an amount of acid solution and leaves standstill 5-30min, magnetic field separation.The product of collecting is with an amount of H
2O and acetone replace washed twice, magnetic field separation.At last, the ferriferous oxide particle and is heated to 70-95 ℃ and stirred 10-60 minute in being dispersed in salts solution, removes remaining acetone.Obtain the ferriferous oxide aqueous dispersions, concentration is 1-10%.
2. formation microemulsion: a certain amount of acrylic amide or acrylic acid or the like hydrophilic monomer, macromolecule crosslink agent are dissolved in the ferriferous oxide aqueous dispersions that step 1 makes, and splash in the micellar system of forming by emulsifying agent and organic solvent, form the reverse micro emulsion of black.
In the above-mentioned steps, the consumption of divalent iron salt accounts for the 0.01-0.50% of whole system weight, and the trivalent iron salt consumption accounts for the 0.02-1.0% of whole system weight.The consumption of emulsifying agent accounts for the 15-35% of whole system weight, and the consumption of deionized water accounts for the 2-10% of whole system weight, and monomeric consumption accounts for the 0.2-10% of whole system weight, and the consumption of linking agent accounts for the 0.008-0.40% of whole system weight.All the other are solvent.
3. initiated polymerization: will be warming up to 20-30 ℃ by the resulting reverse micro emulsion of step 2, logical N in system
2Deoxygenation, with in the initiator adding system, the consumption of initiator is the 0.1-10% of monomer consumption then.Be heated to 50-70 ℃ of initiator system polymerization, after 1-10 minute, system begins polymerization.Maintenance system thermotonus 1-4 hour makes monomer reaction complete, finishes reaction.If system adopts redox system to cause, temperature then remains on 25-40 ℃, and all the other conditions are identical.
Above method makes reverse micro emulsion and directly adds in the excessive water, and the phase reversion of reverse microemulsion liquid system forms the positive microemulsion, and water is 1-10 times of microemulsion volume.Stirring is left standstill the back and with magnet magnetic polymer microsphere is separated, and washes with water then-the magnetic resolution repeated multiple times, and flush away emulsifying agent and organic solvent are dispersed in microballoon with ultrasonic wave at last and have obtained swollen hydrophilic magnetic crosslinked polymer microballoon in the water.The particle diameter of the swollen microsphere that obtains is 80-250nm, and this process is called the phase reversion method again.
Among the present invention, used monomer can be acrylamide (AM), vinylformic acid (AA), methacrylic acid (MAA), sodium acrylate (NaAA), one or more in toxilic acid (MA), the methylene-succinic acid (IA) etc.
Zhi Bei polymkeric substance can be that homopolymer also can be a multipolymer in the present invention.
Among the present invention, two used valency molysite can be iron protochloride (FeCl
24H
2Or ferrous sulfate (FeSO O),
47H
2O) etc.; Trivalent iron salt can be iron(ic) chloride (FeCl
36H
2Or ferric sulfate (Fe O),
2(SO
4)
36H
2O).
Among the present invention, used salt solution can be sodium-acetate (Na
2C
2O
4), Potassium ethanoate (K
2C
2O
4), sodium-chlor solution such as (NaCl) a kind of.
Among the present invention, used alkaline solution can be sodium hydroxide (NaOH), potassium hydroxide (KOH), ammoniacal liquor (NH
4OH) etc. solution is a kind of.
Among the present invention, used acid can be hydrochloric acid (HCl), nitric acid (HNO
3), sulfuric acid (H
2SO
4) wait a kind of.
Among the present invention, used emulsifying agent is anionic emulsifier or cationic emulsifier, serves as better with alkyl ester sulphur salt or alkyl quaternary ammonium salts specifically, as Aerosol OT (AOT), and cetyl trimethylammonium bromide (CTAB) etc.
Among the present invention, used organic solvent is long chain alkane and aromatics alkane, as toluene (Toluene), and benzene (benzene), hexanaphthene (cyclohexane), normal heptane (heptane), kerosene etc.
Among the present invention, initiator can be a thermal initiator, as ammonium persulphate (APS), and Potassium Persulphate (KPS), 2,2 '-azo two (2-amidine propane) hydrochloride (V-50), azo-bis-isobutyl cyanide (AIBN).
The present invention is if carry out in redox initiation system, and the change initiator is a redox initiator, as ammonium persulphate (APS)/N ', and N ', N ', N '-Tetramethyl Ethylene Diamine, or hydrogen peroxide/xitix etc.Be reflected under 25-40 ℃ and carry out.
Among the present invention, linking agent is the macromolecule crosslink agent of using always, as N, and N '-methylene-bisacrylamide (MBA) etc.
In the present invention, the speed that adds alkaline solution can not be too fast, and rate of addition is controlled at was advisable in 0.5-1.5 hour.
The used monomer of the present invention is that effects such as acrylamide monomers such as acrylamide are best.
Two valency molysite and trivalent iron salt mol ratio that the present invention is used are that 1: 2 effect is best.
The used acid of the present invention is that the nitric acid effect is better.
Used emulsifying agent is better with anionic emulsifier Aerosol OT (AOT) among the present invention, this class emulsifying agent low price, applied range, wide material sources.
The particle diameter of the magnetic polymer microsphere of the present invention's preparation is between 70-140nm.The consumption of emulsifying agent can be controlled the particle diameter of magnetic polymer microsphere, and along with the minimizing of emulsifying agent consumption, it is big that microspherulite diameter becomes gradually.
The magnetic saturation intensity of the magnetic polymer microsphere of the present invention's preparation is 1.0-15.0emu/g, and can increase with the increase of ferriferous oxide content, and has superparamagnetism.
Azo-bis-isobutyl cyanide (AIBN), 2, it is better that 2 '-azo two (2-amidine propane) hydrochloride initiators such as (V-50) is applied to thermal initiation system effect of the present invention.
Ammonium persulphate (APS)/N ', N ', N ', N '-Tetramethyl Ethylene Diamine, hydrogen peroxide/xitix etc. are respond well in redox initiation system.
The present invention is in the above-mentioned scope that feeds intake, and polymerization is produced as a kind of nanometer polymer microballoon of polymkeric substance parcel inorganic magnetic material.Its polymkeric substance can be that homopolymer also can be a multipolymer, and inorganic magnetic material is a ferriferous oxide.Size of particles is between the 70-140 nanometer.The magnetic saturation intensity of nm Microsphere of magnetic polymer is 1.0-15.0emu/g, and has superparamagnetism.Can with the phase reversion method with the magnetic polymer microsphere swelling in water, particle diameter is between 80-250nm.
At present, the research of magnetic polymer microsphere mainly lays particular emphasis on submicron or the micron order microballoon that hydrophobic polymer is formed in the world, comparatively speaking, the present invention has following characteristics with the nm Microsphere of magnetic polymer of conversed phase micro emulsion copolymerization preparation: the magnetic polymer microsphere of (1) preparation is a nano-scale, and particle diameter is the 70-140 nanometer.(2) particle diameter of microballoon can be controlled by the consumption of emulsifying agent.(3) polymer microsphere is made of hydrophilic polymer.(4) can with the phase reversion method with crosslinked magnetic polymer microsphere swelling in water, particle diameter is between 80-250nm.(5) preparation method is simple to operate, and stability is high.
Embodiment
Embodiment 1: in the 500ml flask, put into 3.7g FeCl
24H
2O, 10.16g FeCl
36H
2O and 80ml H
2O, logical nitrogen drive oxygen half an hour.40ml 10 molL
-1NaOH solution under mechanical stirring, dropwise add in the iron salt solutions, temperature remains on 25 ℃.After dripping end, continue stirring and also be warming up to 90 ℃ of heating one hour.After heating finished, product was collected with magnetic field separation, and is dispersed in 15ml HNO again
3(2 molL
-1) leave standstill 15min, magnetic field separation in the solution.The product of collecting is being used 50ml H
2O and 200ml acetone replace washed twice, magnetic field separation.At last, Fe
3O
4Particle is being dispersed in 100ml 0.3 molL
-1Sodium acetate soln in, and be heated to 90 ℃ and stir 30min, remove remaining acetone.Obtain concentration and be 6% Fe
3O
4Aqueous dispersions, wherein Fe
3O
4Grain diameter is less than 10nm, and magnetic saturation intensity is 50.5emu/g.
With 0.10g AM, 0.004g MBA is dissolved in 0.50g 6%Fe
3O
4In the aqueous dispersions, dropwise add then in the micellar system of 3.0gAOT and 7.5g toluene, under hyperacoustic dispersion, form the reverse micro emulsion of black.Logical nitrogen drove oxygen 30 minutes, added initiator A IBN 0.01g then, and system is heated to 60 ℃ of initiated polymerizations.Maintenance system thermotonus 2 hours makes monomer reaction complete, finishes reaction.System still is black, and the placement several months still keeps stable.Microspherulite diameter is about 70-75nm.The magnetic saturation intensity of polymer magnetic micro-sphere is 12.1emu/g, and has superparamagnetism.
Making anti-phase fine latex directly adds in the water of 5 times of amounts.Stirring is left standstill the back and with magnet magnetic polymer microsphere is separated, and washes with water then-the magnetic resolution repeated multiple times, and flush away emulsifying agent and organic solvent are dispersed in microballoon in the water with ultrasonic wave at last, have obtained swollen hydrophilic magnetic crosslinked polymer microballoon.The particle diameter of swollen microsphere is 120nm.
Embodiment 2: in the 500ml flask, put into 5.17g FeSO
47H
2O, 9.54g Fe2 (SO
4)
36H
2O and 80mlH
2O, logical nitrogen drive oxygen half an hour.40ml 10 molL
-1NaOH solution under mechanical stirring, dropwise add in the iron salt solutions, temperature remains on 30 ℃.After dripping end, continue stirring and also be warming up to 95 ℃ of heating one hour.After heating finished, product was collected with magnetic field separation, and is dispersed in 15ml HNO again
3(2 molL
-1) leave standstill 15min, magnetic field separation in the solution.The product of collecting is being used 50ml H
2O and 200ml acetone replace washed twice, magnetic field separation.At last, Fe
3O
4Particle is being dispersed in 100ml 0.3 molL
-1Sodium acetate soln in, and be heated to 90 ℃ and stir 30min, remove remaining acetone.Obtain concentration and be 5.9% Fe
3O
4Aqueous dispersions, wherein Fe
3O
4Grain diameter is less than 10nm, and magnetic saturation intensity is 50.5emu/g.
With 0.10g AM, 0.004g MBA is dissolved in 0.50g 5.9%Fe
3O
4In the aqueous dispersions, dropwise add then in the micellar system of 1.5g AOT and 7.5g toluene, under hyperacoustic dispersion, form the reverse micro emulsion of black.Logical nitrogen drove oxygen 30 minutes, added initiator A IBN 0.01g then, and system is heated to 60 ℃ of initiated polymerizations.Maintenance system thermotonus 2 hours makes monomer reaction complete, finishes reaction.System still is black, and the placement several months still keeps stable.Microspherulite diameter is about 125nm.The magnetic saturation intensity of polymer magnetic micro-sphere is 11.6emu/g, and has superparamagnetism.
Making anti-phase fine latex directly adds in the water of 6 times of amounts.Stirring is left standstill the back and with magnet magnetic polymer microsphere is separated, and washes with water then-the magnetic resolution repeated multiple times, and flush away emulsifying agent and organic solvent are dispersed in microballoon in the water with ultrasonic wave at last, have obtained swollen hydrophilic magnetic crosslinked polymer microballoon.The particle diameter of swollen microsphere is 185nm.
Embodiment 3: in the 500ml flask, put into 3.7g FeCl
24H
2O, 10.16g FeCl
36H
2O and 80ml H
2O, logical nitrogen drive oxygen half an hour.40ml 10 molL
-1NaOH solution under mechanical stirring, dropwise add in the iron salt solutions, temperature remains on 15 ℃.After dripping end, continue stirring and also be warming up to 70 ℃ of heating one hour.After heating finished, product was collected with magnetic field separation, and is dispersed in 15ml HNO again
3(2 molL
-1) leave standstill 15min, magnetic field separation in the solution.The product of collecting is being used 50ml H
2O and 200ml acetone replace washed twice, magnetic field separation.At last, Fe
3O
4Particle is being dispersed in 100ml 0.3 molL
-1Sodium acetate soln in, and be heated to 90 ℃ and stir 30min, remove remaining acetone.Add the dilution of an amount of water, obtain concentration and be 1.2% Fe
3O
4Aqueous dispersions, wherein Fe
3O
4Grain diameter is less than 10nm, and magnetic saturation intensity is 50.5emu/g.
With 0.10g AM, 0.004g MBA is dissolved in 0.50g 1.2%Fe
3O
4In the aqueous dispersions, dropwise add then in the micellar system of 3.0g AOT and 7.5g toluene, under hyperacoustic dispersion, form the reverse micro emulsion of black.Logical nitrogen drove oxygen 30 minutes, added initiator A IBN 0.01g then, and system is heated to 70 ℃ of initiated polymerizations.Maintenance system thermotonus 2 hours makes monomer reaction complete, finishes reaction.System still is black, and the placement several months still keeps stable.Microspherulite diameter is 75nm.The magnetic saturation intensity of polymer magnetic micro-sphere is 2.5emu/g, and has superparamagnetism.
Making anti-phase fine latex directly adds in the water of 5 times of amounts.Stirring is left standstill the back and with magnet magnetic polymer microsphere is separated, and washes with water then-the magnetic resolution repeated multiple times, and flush away emulsifying agent and organic solvent are dispersed in microballoon in the water with ultrasonic wave at last, have obtained swollen hydrophilic magnetic crosslinked polymer microballoon.The particle diameter of swollen microsphere is 126nm.
Embodiment 4: in the 500ml flask, put into 5.17g FeSO
47H
2O, 9.54g Fe
2(SO
4)
36H
2O and 80mlH
2O, logical nitrogen drive oxygen half an hour.40ml 10 molL
-1NaOH solution under mechanical stirring, dropwise add in the iron salt solutions, temperature remains on 20 ℃.After dripping end, continue stirring and also be warming up to 75 ℃ of heating one hour.After heating finished, product was collected with magnetic field separation, and is dispersed in 15ml HNO again
3(2 molL
-1) leave standstill 15min, magnetic field separation in the solution.The product of collecting is being used 50ml H
2O and 200ml acetone replace washed twice, magnetic field separation.At last, Fe
3O
4Particle is being dispersed in 100ml 0.3 molL
-1Sodium acetate soln in, and be heated to 90 ℃ and stir 30min, remove remaining acetone.Obtain concentration and be 5.9% Fe
3O
4Aqueous dispersions, wherein Fe
3O
4Grain diameter is less than 10nm, and magnetic saturation intensity is 50.5emu/g.
With 0.09g AM and 0.01g IA, 0.004g MBA is dissolved in 0.50g 6%Fe
3O
4In the aqueous dispersions, dropwise add then in the micellar system of 3.0g AOT and 7.5g toluene, under hyperacoustic dispersion, form the reverse micro emulsion of black.Logical nitrogen drove oxygen 30 minutes, added initiator A IBN 0.01g then, and system is heated to 60 ℃ of initiated polymerizations.Maintenance system thermotonus 2 hours makes monomer reaction complete, finishes reaction.System still is black, and the placement several months still keeps stable.Microspherulite diameter is about 80nm.The magnetic saturation intensity of polymer magnetic micro-sphere is 11.8emu/g, and has superparamagnetism.
Making anti-phase fine latex directly adds in the water of 6 times of amounts.Stirring is left standstill the back and with magnet magnetic polymer microsphere is separated, and washes with water then-the magnetic resolution repeated multiple times, and flush away emulsifying agent and organic solvent are dispersed in microballoon in the water with ultrasonic wave at last, have obtained swollen hydrophilic magnetic crosslinked polymer microballoon.The particle diameter of swollen microsphere is 180nm.
Claims (13)
1, a kind of nm Microsphere of magnetic polymer, it is characterized in that the polymkeric substance that produces with acrylic amide and the polymerization of acrylic acid or the like hydrophilic monomer is an integument, with the inorganic magnetic material ferriferous oxide is nuclear, earlier by the synthetic ferriferous oxide inorganic microspheres of solution precipitation, use conversed phase micro emulsion copolymerization method synthesizing magnetic polymer microballoon again, its particle diameter is the 70-140 nanometer, and magnetic saturation intensity is 1.0-15.0emu/g, and has superparamagnetism.
2, nm Microsphere of magnetic polymer according to claim 1 is characterized in that the used polymer monomer of integument is one or more of acrylamide, methacrylic acid, vinylformic acid, sodium acrylate, toxilic acid, methylene-succinic acid.
3, nm Microsphere of magnetic polymer according to claim 1 and 2, it is characterized in that examining ferriferous oxide is divalent iron salt and trivalent iron salt.
4, the preparation method of the described nm Microsphere of magnetic polymer of a kind of claim 1 is characterized in that concrete steps are as follows:
(1) the synthetic ferriferous oxide inorganic microspheres of solution deposit: two valency molysite and trivalent iron salt are soluble in water, and the mol ratio of two valency molysite and trivalent iron salt is 0.5-5.0, and logical nitrogen drives oxygen, 10-100 minute; Alkaline solution dropwise adds under mechanical stirring in the iron salt solutions slowly, and temperature remains on 15-30 ℃; After dripping end, continue stirring and also be warming up to 70-95 ℃ of heating 0.5-3.0 hour, keep the nitrogen oxygen-free environment in the adition process always; After heating finished, product was collected with magnetic field separation, and was dispersed in again and leaves standstill 5-30min, magnetic field separation in the acid solution; The product of collecting is being used H
2O and acetone replace washed twice, magnetic field separation; At last, the ferriferous oxide particle and is heated to 70-95 ℃ and stirred 10-60 minute in being dispersed in salts solution, removes remaining acetone; Obtain the ferriferous oxide aqueous dispersions, concentration is 1-10%;
(2) form microemulsion: a certain amount of acrylic amide or acrylic acid or the like hydrophilic monomer, macromolecule crosslink agent are dissolved in the ferriferous oxide aqueous dispersions that step 1 makes, and splash in the micellar system of forming by emulsifying agent and organic solvent, form the reverse micro emulsion of black;
In the above-mentioned steps, the consumption of divalent iron salt accounts for the 0.01-0.50% of whole system weight, the trivalent iron salt consumption accounts for the 0.02-1.0% of whole system weight, the consumption of emulsifying agent accounts for the 15-35% of whole system weight, the consumption of deionized water accounts for the 2-10% of whole system weight, monomeric consumption accounts for the 0.2-10% of whole system weight, and the consumption of linking agent accounts for the 0.008-0.40% of whole system weight, and all the other are solvent;
(3) initiated polymerization: will be warming up to 20-30 ℃ by the resulting reverse micro emulsion of step 2, logical N in system
2Deoxygenation, with in the initiator adding system, the consumption of initiator is the 0.1-10% of monomer consumption then; Be heated to 50-70 ℃ of initiator system polymerization, after 1-10 minute, system begins polymerization; Maintenance system thermotonus 1-4 hour makes monomer reaction complete, finishes reaction.If system adopts redox system to cause, temperature then remains on 25-40 ℃, and all the other conditions are identical.
5, according to the preparation method of the described nm Microsphere of magnetic polymer of claim 4, carry out if be reflected in the redox system, temperature of reaction is 25-40 ℃.
6,, it is characterized in that used monomer is one or more of acrylamide, vinylformic acid, methacrylic acid, sodium acrylate, toxilic acid, methylene-succinic acid according to the preparation method of claim 4 or 5 described nm Microsphere of magnetic polymer.
7, according to the preparation method of claim 4 or 5 described nm Microsphere of magnetic polymer, it is characterized in that two used valency molysite are iron protochloride or ferrous sulfate, trivalent iron salt is iron(ic) chloride or ferric sulfate.
8,, it is characterized in that used alkaline solution is a kind of of sodium hydroxid, potassium hydroxide, ammoniacal liquor according to the preparation method of claim 4 or 5 described nm Microsphere of magnetic polymer.
9,, it is characterized in that used organic solvent is long chain alkane or aromatics alkane according to the preparation method of claim 4 or 5 described nm Microsphere of magnetic polymer.
10,, it is characterized in that used emulsifying agent is alkyl ester sulfonate or alkyl quaternary ammonium salts according to the preparation method of claim 4 or 5 described nm Microsphere of magnetic polymer.
11, according to the preparation method of the described nm Microsphere of magnetic polymer of claim 4, it is characterized in that the thermal initiator that reacts used is an azo-bis-isobutyl cyanide, or 2,2 '-azo two (2-amidine propane) hydrochloride.
12, according to the preparation method of the described nm Microsphere of magnetic polymer of claim 5, it is characterized in that reacting used redox initiator is ammonium persulphate/N ', N ', N ', N '-Tetramethyl Ethylene Diamine, or hydrogen peroxide/xitix.
13, according to the preparation method of claim or 4 or 5 described nm Microsphere of magnetic polymer, it is characterized in that reacting used linking agent is N ', N '-methylene-bisacrylamide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336584C (en) * | 2004-12-02 | 2007-09-12 | 同济大学 | Tungsten trioxide/polymer nano core-shell microsphere and preparing process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6962685B2 (en) * | 2002-04-17 | 2005-11-08 | International Business Machines Corporation | Synthesis of magnetite nanoparticles and the process of forming Fe-based nanomaterials |
| CN1990528B (en) * | 2005-12-26 | 2010-06-16 | 中国科学院成都有机化学有限公司 | Method for functionalization on magnetic nano particle surface |
| WO2007136700A2 (en) * | 2006-05-17 | 2007-11-29 | The University Of Akron | Method of purifying block copolymers |
| CN1862725B (en) * | 2006-06-12 | 2010-05-12 | 南京航空航天大学 | Chemical deposition of fine magnetic element and electrochemical deposition manufacturing method and system |
| CN103992433B (en) * | 2014-04-22 | 2016-03-23 | 成都理工大学 | A kind of preparation method of high strength high-temperature resistant polymer nano-microspheres |
| CN106552296B (en) * | 2015-09-29 | 2020-08-14 | 上海氪励铵勤科技发展有限公司 | Nano particles, preparation method thereof, calculus removing device and application |
| CN110734524A (en) * | 2018-07-18 | 2020-01-31 | 苏州为度生物技术有限公司 | Preparation method of cationic polymer modified magnetic shell-core microsphere |
| CN109653215A (en) * | 2018-12-14 | 2019-04-19 | 沈阳建筑大学 | A kind of application method of the reinforcing slurries with magnetosensitive thickening power |
| CN111995720B (en) * | 2020-08-18 | 2021-09-21 | 燕山大学 | Monodisperse superparamagnetic carboxyl silicon magnetic bead and preparation method thereof |
| CN115710373B (en) * | 2022-11-22 | 2023-07-28 | 东南大学 | Preparation method of hydrogel magnetic microsphere |
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2001
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336584C (en) * | 2004-12-02 | 2007-09-12 | 同济大学 | Tungsten trioxide/polymer nano core-shell microsphere and preparing process thereof |
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