CN101838426A - Synthesis method of superparamagnetic polymer microspheres - Google Patents
Synthesis method of superparamagnetic polymer microspheres Download PDFInfo
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- CN101838426A CN101838426A CN 201010168903 CN201010168903A CN101838426A CN 101838426 A CN101838426 A CN 101838426A CN 201010168903 CN201010168903 CN 201010168903 CN 201010168903 A CN201010168903 A CN 201010168903A CN 101838426 A CN101838426 A CN 101838426A
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- magnetic
- alkylene
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Abstract
The invention relates to a synthesis method of superparamagnetic polymer microspheres, which mainly comprises the following steps: preparing superparamagnetic Fe3O4 the surface of which is coated with a hydrophobic layer; preparing hydrophobic alkylene Fe3O4 magnetic fluid; preparing nonmagnetic seed particles; mixing and swelling the hydrophobic alkylene Fe3O4 magnetic fluid and the nonmagnetic seed particles; and preparing the magnetic polymer microspheres through initiated polymerization. The innovative points are as follows: the hydrophobic alkylene Fe3O4 magnetic fluid and the nonmagnetic seed particles are mixed and swelled. The method has simple preparation process, convenient operation and high yield; and the synthesized magnetic polymer microsphere has narrow size distribution, strong magnetism and stable chemical property.
Description
Technical field
The present invention relates to a kind of synthetic method of microballs of super-paramagnetic polymer.
Background technology
Magnetic polymer microsphere is as a kind of novel carrier of separating, it integrates magnetic and affine isolating advantage, can be fast and convenient and highly selective from the living things system of complexity, isolate target biological molecules, having tempting application prospect in biomedicines such as immobilized enzyme, cell divide, immunodetection, targeted drug and affine separation and biochemical engineering field, is current one of the prospective research topic that has.The method of prior art synthesizing magnetic polymer microballoon mainly contains polymer entrapping method, interface sedimentation and monomer polymerization method etc.Monomer polymerization method comprises that the suspension polymerization of magnetic-particle under existing is (referring to Lee Y, Rho J, Jung B, Preparation ofMagnetic Ion-Exchange Resins by the Suspension Polymerization of Styrene withMagnetite, J.Appl.Polym.Sci., 2003,89,2058), letex polymerization is (referring to Yanase N, Noguchi H, Asakura H, Suzuta T, Preparation of Magnetic Latex Particles by EmulsionPolymerization of Styrene in the Presence of a Ferrofluid, J.Appl.Polym.Sci., 1993,50,765.), dispersion polymerization is (referring to HorAK D, Magnetic Polyglycidylmethacrylate Microspheresby Dispersion Polymerization, J.Polym.Sci.Part A Polym.Chem., 2001, method such as 39,3707.).
But the preparation and the applied research of magnetic macromolecular microsphere at present also exists some shortcomings.The magnetic microsphere of entrapping method preparation for example, the microspherulite diameter of gained distributes wide, out-of-shape, particle diameter is difficult to control, and magnetic content is also inconsistent in the different microballoons, and the strong and weak difference of the magnetic of each microballoon is very big; And the magnetic microsphere size of conventional suspension polymerization preparation arrives between the hundreds of micron tens usually, and specific surface area is little, and particle size distribution is wide; The particle diameter of the magnetic microsphere of emulsion polymerization preparation is too little, and magnetic content is very low, even in use adopt very high externally-applied magnetic field, also is difficult to separate; The magnetic content of the magnetic microsphere of dispersion copolymerization method preparation is low, and the magnetic content distribution between each microballoon is inhomogeneous, and the magnetic content of the microballoon that has is almost nil; The Ugelstad method close with the present invention (referring to Ugelstad J, Ellingsen T, Berge A, Helgee B.Magnetic polymerparticles.WO 8303920,1983) preparation process is very complicated, and productive rate is low, be unfavorable for amplifying and produce, commodity price is expensive especially.
Summary of the invention
For overcoming the defective that exists on the above-mentioned magnetic polymer microsphere manufacture method, the present invention proposes a kind of method of synthesizing magnetic polymer microballoon, this method preparation process is simple, easy to operate, productive rate is high, and magnetic polymer microsphere narrow diameter distribution, the magnetic that synthesizes is strong, chemical property is stable.
Main contents of the present invention are as follows:
To adopting the nanometer Fe of chemical coprecipitation preparation
3O
4Particle surface has carried out the hydrophobic layer coating, and it is dissolved in makes stable magnetic fluid in the hydrophobicity vinyl monomer and form oil phase.One or more vinyl monomers are made non magnetic seed grain, and form water.With oil phase and water fully shake mix swelling after, microballs of super-paramagnetic polymer is prepared in the re-initiation polymerization.The magnetic polymer microsphere that synthesizes has advantages such as particle diameter is controlled, magnetic strong, the magnetic homogeneity is good.
Concrete steps of the present invention are as follows:
(1) the preparation surface is coated with the superparamagnetism Fe of hydrophobic layer
3O
4Particle.Coated magnetic Fe wherein
3O
4Particle has nuclear/shell-type structure, and hydrophobic layer is C
8-22Straight chain fatty acid.
(2) preparation hydrophobicity alkylene Fe
3O
4Magnetic fluid.With above-mentioned magnetic Fe
3O
4Particles dispersed is dissolved in the hydrophobicity vinyl monomer, makes the alkylene magnetic fluid, magnetic Fe
3O
4Particle and olefinic monomer volume ratio are 1: 2 to 1: 10.
(3) prepare non magnetic seed grain.It is by one or more vinyl monomer homopolymerizations or copolymerization synthetic polymkeric substance.Its synthetic method comprises suspension polymerization, dispersion polymerization, letex polymerization, mini-emulsion polymerization etc.Synthetic seed particulate vinyl monomer comprises styrenic, divinylbenzene class, (methyl) esters of acrylic acid, vinyl esters etc. and derivative thereof.Polymer monomer and linking agent volume ratio are 10: 1 to 20: 1,0.01% to 0.5% of initiator amount cumulative volume.
(4) magnetic fluid mixes swelling with non magnetic seed grain.Be with aforesaid hydrophobicity alkylene Fe
3O
4Magnetic fluid is as oil phase, and non magnetic seed grain is made solution as water, and oil phase and water are fully shaken mixing 24 hours to 36 hours, forms the swelling system that magnetic fluid is adsorbed on the seed microsphere surface, is absorbed fully until magnetic fluid to obtain the swelling product.
(5) initiated polymerization prepares magnetic polymer microsphere.Be in aforesaid swelling product, add the initiator initiated polymerization, synthesize the monodisperse superparamagnetic polymer beads.Wherein initiator amount accounts for 0.1% to 3% of cumulative volume, and dosage of crosslinking agent accounts for 1% to 10% of cumulative volume.
The magnetic polymer microsphere inside that this method synthesizes, the clad nano magnetic Fe
3O
4The particle high dispersing has inorganic particle and organic polymer uniform composite structure on the nanoscale in polymer microballoon, have superparamagnetism; The magnetic polymer microsphere particle diameter between 0.01-5 μ m, controllable granularity and distribution relative narrower, magnetic Fe
3O
4The weight ratio that accounts for whole microballoon is 0.5-55%, the strong and distribution homogeneous of magnetic, and chemical property is stable, acid and alkali-resistance.
Embodiment
Below by embodiment technical scheme of the present invention is further described:
Embodiment 1.
(1) in filling the 1L reactor of 500ml deionized water, add 0.086 mole of iron(ic) chloride and 0.043 mole of iron protochloride, feed nitrogen protection, be warming up to 80 ℃.The NH of instantaneous impouring 25%
3H
2O 27-29ml fully after the vigorous stirring, dropwise adds oleic acid at once, till can seeing clear liquid, continues constant temperature and stirs 30 minutes.After the magnet magnetic resolution, clean repeatedly through deionized water, obtain black bulk magnetic Fe
3O
4Particle.
(2) contain in the there-necked flask of solution of 0.25%SDS at 50ml, add the 5ml styrene monomer and a certain amount of before the magnetic Fe of oleic acid-coated of preparation
3O
4Particle, 25 ℃ of fully emulsified 6h of sonic oscillation form the oil phase magnetic fluid.
(3) add 100ml distilled water in the 500ml there-necked flask, styrene monomer that 9.75mlNaOH handled and the Vinylstyrene of 0.545ml (DVB), ultra-sonic dispersion 30min fully stir the back and lead to nitrogen except that deoxidation, warming-in-water to 70 ℃.Add the 40mlKPS aqueous solution that is dissolved with the 0.05g initiator behind the temperature-stable, initiated polymerization time 16h cools to 60 ℃, slaking 2h.Polymer product cooling is after the whizzer centrifugation, and the deionized water repetitive scrubbing is dispersed in the water again, obtains the crosslinked PSt-DVB polymer microballoon of water.
(4) with above-mentioned oil phase (2) and water (3), mechanical stirring is mixed, abundant swelling 24h under 25 ℃ of conditions.
(5) the initiator benzoyl peroxide (BPO) of adding 0.3g in above-mentioned swelling system, the 80% linking agent Vinylstyrene of handling through NaOH (DVB) of 1ml feeds nitrogen, mixes above-mentioned emulsion and be warming up to 70 ℃ in the 500ml there-necked flask, constant temperature polymerization 12h is cooled to 60 ℃ of slaking 2h.
The polymerization cooling is after magnetic resolution behind the distilled water repetitive scrubbing, obtains the PSt magnetic polymer microsphere.
Embodiment 2.
(1) in the 1L stirring reactor that fills 500ml distilled water, adds 0.086 mole of FeCl
24H
2O and 0.173 mole of FeCl
36H
2O is warming up to 90 ℃, and impouring contains 0.956 mole of NH
3H
2The O aqueous solution gets started by the speed of 0.5ml/min and drips the about 15ml of linolenic acid, until seeing one clearly till the supernatant liquor, and continuation constant temperature 1 hour, the supernatant liquor that inclines can obtain black lumps coated magnetic Fe
3O
4The particle aggregation body.
(2) in the there-necked flask of 500ml, add 95ml methyl methacrylate (MMA) monomer and a certain amount of linolenic magnetic Fe of coating of preparation before
3O
4Particle, sonic oscillation mixes, and forms the oil phase magnetic fluid.
(3) be equipped with at 1L and add the 620ml deionized water in the four-hole boiling flask of reflux condensing tube, nitrogen inlet, mechanical stirring and charging opening, in the water bath with thermostatic control with 60 ℃ of its immigrations, after stirring logical nitrogen 10min, add 65g MMA monomer and 1.3g linking agent DVB, continue to stir logical nitrogen 30min.Add Potassium Persulphate (KPS) aqueous solution 30ml (containing KPS 0.65g) of deoxidation then, carry out polyreaction.Be reflected at 60 ℃ carry out 24h after, be cooled to room temperature, polymer emulsion is used the deionized water repetitive scrubbing through the centrifugal polymer microsphere that obtains.Get 15ml seed microballoon emulsion and join 50ml and contain in the solution of 0.25%gSDS, 25 ℃ of fully emulsified 6h of ultrasonic vibration form waters.
(4) with above-mentioned oil phase (2) and water (3), mechanical stirring is mixed, abundant swelling 24h under 25 ℃ of conditions.
(5) in above-mentioned swelling system, add the 80% linking agent divinylbenzene of handling through NaOH (DVB) of 5ml and the initiator benzoyl peroxide (BPO) of 5g, feed nitrogen, mix above-mentioned emulsion and be warming up to 80 ℃ in the 500ml there-necked flask, constant temperature polymerization 12h is cooled to 60 ℃ of slaking 2h.
The polymerization cooling is after magnetic resolution behind the distilled water repetitive scrubbing, obtains the PMMA magnetic polymer microsphere.
Embodiment 3.
(1) in filling 1 liter of stirring reactor of 700ml distilled water, adds 0.21 mole of FeCl
24H
2O and 0.31 mole of FeCl
36H
2O is warming up to 70 ℃, and impouring 100ml contains 1 mole NaHCO
3The aqueous solution gets started by the speed of 0.5ml/min and drips the about 20ml of stearic acid, until seeing one clearly till the supernatant liquor, and continuation constant temperature 1 hour, the supernatant liquor that inclines can obtain black lumps bag and tie up magnetic Fe 3O4 particle aggregation body.
(2) in the there-necked flask of 500ml, with the stearic Fe of above-mentioned coating
3O
4Particle is dissolved in an amount of 100ml toluene, is stirred to dissolving fully, forms the oil base magnetic fluid of tolyl.
(3) adopt dispersion copolymerization method earlier, in the 250ml four-hole bottle, add 81g ethanol and 9g water, add 2g stablizer PVP K-30 again, being stirred to it dissolves fully, then add 10g monomer St and 0.1g initiator A IBN, stir down logical nitrogen 30min after, reactor put into is preheating to 70 ℃ water bath with thermostatic control, keep nitrogen atmosphere, 200rpm rotating speed reaction 12h down makes PSt seed microballoon; After in the above-mentioned PSt seed microballoon that makes, adding the suitable quantity of water dilution, add comonomer 2ml St, 4ml HEMA, 0.2ml linking agent EGDMA and 0.12g initiator A IBN, mixed solution at room temperature stirs 24h, and monomer and linking agent are absorbed by the seed microballoon fully.Last this mixed solution is at 70 ℃, and nitrogen atmosphere is reaction 12h down, makes polystyrene-hydroxyethyl methylacrylate (P (St-HEMA)) crosslinked microsphere of water.
(4) with above-mentioned oil phase (2) and water (3), mechanical stirring is mixed, abundant swelling 36h under 25 ℃ of conditions.
(5) add a certain amount of linking agent EGDMA and initiator A IBN in above-mentioned swelling system, feed nitrogen, mix above-mentioned emulsion and be warming up to 70 ℃ in the 500ml there-necked flask, constant temperature polymerization 18h is cooled to 60 ℃ of slaking 2h.
The polymerization cooling is after magnetic resolution behind the distilled water repetitive scrubbing, obtains P (St-HEMA) magnetic polymer microsphere.
Claims (5)
1. the method for a synthetic microballs of super-paramagnetic polymer, described method comprises following concrete steps:
1.1 the preparation surface is coated with the superparamagnetism Fe of hydrophobic layer
3O
4: described coated magnetic Fe
3O
4Particle has nuclear/shell-type structure, and hydrophobic layer is C
8-22Straight chain fatty acid;
1.2 preparation hydrophobicity alkylene Fe
3O
4Magnetic fluid: the superparamagnetism Fe that step 1.1 is made
3O
4Particles dispersed is dissolved in the hydrophobicity vinyl monomer, makes hydrophobicity alkylene Fe
3O
4Magnetic fluid;
1.3 prepare non magnetic seed grain:, make non magnetic seed grain with one or more vinyl monomer homopolymerizations or copolymerization synthetic polymer;
It is characterized in that described method also comprises the steps:
1.4 with hydrophobicity alkylene Fe
3O
4Magnetic fluid mixes swelling with non magnetic seed grain: the hydrophobicity alkylene Fe that step 1.2 is made
3O
4Magnetic fluid is as oil phase, step 1.3 is made non magnetic seed grain make solution as water, oil phase and water are fully shaken mixing 24 hours to 36 hours, formation hydrophobicity alkylene magnetic fluid is adsorbed on the swelling system of non magnetic seed grain microsphere surface, is absorbed fully until hydrophobicity alkylene magnetic fluid to obtain the swelling product;
1.5 initiated polymerization prepares the step of magnetic polymer microsphere: in the swelling product that step 1.4 makes, add the initiator initiated polymerization, synthesize the monodisperse superparamagnetic polymer beads.
2. the method for a kind of synthetic microballs of super-paramagnetic polymer according to claim 1 is characterized in that: in the described step 1.2, and superparamagnetism Fe
3O
4Particle and vinyl monomer volume ratio are 1: 2 to 1: 10.
3. the method for a kind of synthetic microballs of super-paramagnetic polymer according to claim 1, it is characterized in that: in the described step 1.3, the synthetic method of the non magnetic seed grain of described preparation comprises suspension polymerization, dispersion polymerization, letex polymerization, mini-emulsion polymerization.
4. the method for a kind of synthetic microballs of super-paramagnetic polymer according to claim 1, it is characterized in that: in the described step 1.3, polymer monomer and linking agent volume ratio are 10: 1 to 20: 1,0.01% to 0.5% of initiator amount cumulative volume.
5. the method for a kind of synthetic microballs of super-paramagnetic polymer according to claim 1, it is characterized in that: in the described step 1.5, initiator amount accounts for 0.1% to 3% of cumulative volume, and dosage of crosslinking agent accounts for 1% to 10% of cumulative volume.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984096A (en) * | 2010-11-15 | 2011-03-09 | 北京科技大学 | Method for extracting noble metal ions by using magnetic medium |
| CN104211851A (en) * | 2014-09-24 | 2014-12-17 | 天津大学 | Preparation method of monodisperse macromolecule composite magnetic microspheres |
| CN105061962A (en) * | 2015-09-15 | 2015-11-18 | 苏州凯欧曼新材料科技有限公司 | Magnetic composition and preparation method thereof |
| CN107552022A (en) * | 2017-05-02 | 2018-01-09 | 四川大学 | A kind of star magnetic response organic adsorption material and preparation method thereof |
| CN108636366A (en) * | 2018-04-17 | 2018-10-12 | 江苏国创环保科技有限公司 | A kind of preparation method and application of the magnetic adsorptive material of absorption heavy metal |
| CN110732296A (en) * | 2018-07-18 | 2020-01-31 | 苏州为度生物技术有限公司 | Preparation method of magnetic microspheres with fluffy shell layers |
| CN115228450A (en) * | 2022-07-12 | 2022-10-25 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5599889A (en) * | 1994-08-16 | 1997-02-04 | Stoever; Harald D. H. | Method of forming polymer microspheres |
| WO1999019000A1 (en) * | 1997-10-11 | 1999-04-22 | The Research Foundation Of State University Of New York | Controlled size polymeric microspheres with superparamagnetic cores |
| CN1253147A (en) * | 1998-11-10 | 2000-05-17 | 中国科学院化工冶金研究所 | Microballs of super-paramagnetic polymer and preparing process thereof |
| US6133047A (en) * | 1996-05-24 | 2000-10-17 | Bio Merieux | Superparamagnetic monodisperse particles |
| CN1375507A (en) * | 2001-03-20 | 2002-10-23 | 清华大学 | Surface cladding and radical functino modification method of magnetic microsphere, thus obtained microsphere and its application |
| CN1468898A (en) * | 2003-07-02 | 2004-01-21 | 北京倍爱康生物技术股份有限公司 | Prepn of super-paramagnetic polymer microsphere |
-
2010
- 2010-05-05 CN CN2010101689032A patent/CN101838426B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5599889A (en) * | 1994-08-16 | 1997-02-04 | Stoever; Harald D. H. | Method of forming polymer microspheres |
| US6133047A (en) * | 1996-05-24 | 2000-10-17 | Bio Merieux | Superparamagnetic monodisperse particles |
| WO1999019000A1 (en) * | 1997-10-11 | 1999-04-22 | The Research Foundation Of State University Of New York | Controlled size polymeric microspheres with superparamagnetic cores |
| CN1253147A (en) * | 1998-11-10 | 2000-05-17 | 中国科学院化工冶金研究所 | Microballs of super-paramagnetic polymer and preparing process thereof |
| CN1375507A (en) * | 2001-03-20 | 2002-10-23 | 清华大学 | Surface cladding and radical functino modification method of magnetic microsphere, thus obtained microsphere and its application |
| CN1468898A (en) * | 2003-07-02 | 2004-01-21 | 北京倍爱康生物技术股份有限公司 | Prepn of super-paramagnetic polymer microsphere |
Non-Patent Citations (1)
| Title |
|---|
| 《中国科学 B辑》 20040820 阳承利，官月平等 磁性PMMA微球的制备与表面修饰 265-269 1-5 第34卷, 第4期 2 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101984096A (en) * | 2010-11-15 | 2011-03-09 | 北京科技大学 | Method for extracting noble metal ions by using magnetic medium |
| CN101984096B (en) * | 2010-11-15 | 2012-05-09 | 北京科技大学 | Method for extracting noble metal ions by using magnetic medium |
| CN104211851A (en) * | 2014-09-24 | 2014-12-17 | 天津大学 | Preparation method of monodisperse macromolecule composite magnetic microspheres |
| CN104211851B (en) * | 2014-09-24 | 2016-08-24 | 天津大学 | A kind of preparation method of mono-disperse polymer composite magnetic microballoon |
| CN105061962A (en) * | 2015-09-15 | 2015-11-18 | 苏州凯欧曼新材料科技有限公司 | Magnetic composition and preparation method thereof |
| CN107552022A (en) * | 2017-05-02 | 2018-01-09 | 四川大学 | A kind of star magnetic response organic adsorption material and preparation method thereof |
| CN107552022B (en) * | 2017-05-02 | 2019-12-27 | 四川大学 | Star-shaped magnetic response organic adsorption material and preparation method thereof |
| CN108636366A (en) * | 2018-04-17 | 2018-10-12 | 江苏国创环保科技有限公司 | A kind of preparation method and application of the magnetic adsorptive material of absorption heavy metal |
| CN110732296A (en) * | 2018-07-18 | 2020-01-31 | 苏州为度生物技术有限公司 | Preparation method of magnetic microspheres with fluffy shell layers |
| CN110732296B (en) * | 2018-07-18 | 2021-09-03 | 苏州为度生物技术有限公司 | Preparation method of magnetic microspheres with fluffy shell layers |
| CN115228450A (en) * | 2022-07-12 | 2022-10-25 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
| CN115228450B (en) * | 2022-07-12 | 2023-10-17 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
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