CN100412093C - Prepn. of magnetic molecular pellets by complex emulsion process (W1/0/W2 type) - Google Patents
Prepn. of magnetic molecular pellets by complex emulsion process (W1/0/W2 type) Download PDFInfo
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Abstract
The present invention provides a novel method for preparing magnetic polymer microspheres. The method adopts an emulsion compounding method to prepare magnetic polymer microspheres, the particle diameter of the prepared magnetic polymer microspheres is from 50 nanometers to 800 micrometers, and magnetic particles embedded in the microsphere account for 0.5% to 50% of the weight of the whole magnetic polymer microsphere. The method comprises the main steps: preparing initial emulsion, compounding emulsion, adding alkaline, removing organic solvents, solidifying the drops of the compound emulsion, washing and separating magnetic microspheres, drying the magnetic microspheres, etc. The present invention is characterized in that firstly, the compound emulsion in which a malysite solution is embedded is prepared by the emulsion compounding method; secondly, organic alkali or inorganic alkali is added to the compound emulsion to enable the molysite to be converted into magnetic particles; finally, the drops of the compound emulsion are solidified to obtain the magnetic polymer microspheres. The particle diameter of the magnetic polymer microspheres can be controlled by the viscosity of the initial emulsion, the rotation speed of external water phases in the compound emulsion and the concentration of stabilizing agents for the external water phases; the magnet content can be controlled by the concentration of the solute of internal water phases and the proportion of the volume of the internal water phases to the volume of oil phases. The magnetic polymer microspheres can be used as carriers for various enzymes, antibodies and targeted drugs, and can be widely used in the fields of cell separation, clinical diagnosis, target drug carries, immobilized enzymes, affinity and separation, etc. The present invention has the characteristics of simple method, good repeatability, easy raw material obtainmnet, low cost, controllable particle diameter of the microspheres, uniform.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to magnetic macromolecular microsphere that has magnetic and preparation method thereof.
Technical background
Magnetic macromolecular microsphere is meant by appropriate means magnetic-particle to be embedded in the polymer microsphere and forms the microballoon with certain magnetic responsiveness and special construction.It is a kind of new function polymer composite that grows up in the later stage seventies 20th century.On the one hand, it has the characteristic of polymer microsphere, can make polymer microsphere surface have multiple functional group by chemical reactions such as copolymerization, surface modifications, thereby can be in conjunction with multiple biologically active substance; On the other hand, it has magnetic again, can be fast under externally-applied magnetic field and other do not have the separating substances of magnetic, and energy expenditure is little.Therefore, magnetic macromolecular microsphere has a wide range of applications in the fields such as contrast medium of biomedical (clinical diagnosis, targeted drug), cytology (cellular segregation), immobilized enzyme, affine separation and magnetic resonance image (MRI) as new functional macromolecule material.
At present, the preparation method of existing magnetic macromolecular microsphere has four kinds in document and the patent: suspension polymerization
[1,2,3], the activation swelling method
[4,5], the interface sedimentation
[6,7], the reverse microemulsion method
[8,9](1) suspension polymerization or emulsion--solvent evaporated method, with magnetic fluid or magnetic small-particle be dispersed in make mixing solutions in macromolecular solution or the monomer after, this mixing solutions and water are mixed and made into O/W type (oil-in-water-type) emulsion, adopt then to take out and desolvate or the method for polymerization single polymerization monomer obtains solidified microsphere.Its shortcoming is that the affinity between magnetic-particle and the macromolecular material is poor, and the wetting ability of magnetic-particle is strong, at monomer polymerization or take out when desolvating, the magnetic small-particle escapes into surface and outer aqueous phase easily, not only embedding rate is low, and microsphere surface adsorbing a large amount of magnetic-particles, is difficult to wash-out, be used for that biologically active substance separates or fixedly the time, influence the activity of biologically active substance.(2) activation swelling method, the activation swelling method of Ugelstad proposition in 1993 is the better method of the preparation magnetic macromolecular microsphere of hitherto reported.Concrete steps are after preparing poly-(vinylbenzene-2-hydroxyethyl meth acrylate) microballoon of single-size with emulsion polymerization, to make bigger microballoon with swelling method more then.Then, vinylbenzene is nitrated, utilize the affinity interaction of nitro and iron ion again, make microballoon absorb the ferrous iron and the ferric ion aqueous solution.After the microballoon that has adsorbed iron ion separated, mix, make the iron ion in the microballoon be converted to Fe with basic solution
3O
4Particle and being deposited in the microballoon.But problems such as length consuming time, reactions steps are many, severe reaction conditions that this method exists, thus cause cost too high, therefore limited magnetic macromolecular microsphere in biochemical industry, medicine industry and application clinically.(3) interface sedimentation makes the magnetic small-particle of positively charged be adsorbed on electronegative polymer microsphere surface earlier, and then plates one deck macromolecular material on its surface.Because a polymer microsphere surface can only adsorb one deck magnetic-particle, the embedding amount of magnet is very low.(4) reverse microemulsion process, in redox or thermal initiation system, to hydrophilic monomers such as acrylic amide and acrylic acid or the like, the molysite that adds emulsifying agent, initiator, linking agent, different valence state, control is reflected in certain scope that feeds intake, directly synthetic magnetic macromolecular microsphere with superparamagnetism of a step in reverse micro emulsion.But this method only is applicable to hydrophilic monomer, the particle diameter of microballoon also smaller (below 200nm), and reaction conditions is also wayward.In sum, existing preparation method only is applicable to laboratory or Small Scale Industry production, therefore, is necessary to develop the new method for preparing magnetic macromolecular microsphere, in the hope of the higher magnetic macromolecular microsphere of preparation cost performance.
Desirable magnetic macromolecular microsphere microballoon should have following characteristics: magnetic-particle has superparamagnetism; The microspherulite diameter homogeneous; Microballoon contains quantity of magnetism height; Chemical stability is good, and magnetic-particle does not have leakage, and is pollution-free; The physical strength height; Good biocompatibility; Technology is simple, good reproducibility, is easy to large-scale production, and price is low.
To the introduction of prior preparation method, be not difficult to find out that the microballoon that does not have a kind of method preparation in the existing method can reach the requirement of desirable microballoon by above, this has also limited the application of magnetic macromolecular microsphere in medical treatment and bioseparation.The invention provides a kind of novel preparation method---compound emulsion method, in the hope of reach the preparation desirable magnetic macromolecular microsphere requirement, thereby produce great economic benefit and social benefit.
Summary of the invention
The invention provides a kind of preparation method of novel magnetic macromolecular microsphere.This method uses compound emulsion method to prepare magnetic macromolecular microsphere, and the magnetic macromolecular microsphere particle size range of preparation is 50nm～800 μ m.The mass ratio that the magnetic-particle of microballoon institute embedding accounts for whole microballoon is 0.5%～50%.The curing of the adding of the preparation that its main technique flow process is the colostrum emulsion, emulsionization, alkali, the removal of organic solvent and emulsion drop, the washing of magnetic microsphere and separate, microballoon drying etc.It is characterized in that preparing earlier the emulsion emulsion of inner embedding iron salt solutions, and then add organic bases or mineral alkali makes molysite be converted into magnetic-particle, again the emulsion emulsion droplet is solidified, prepare magnetic macromolecular microsphere with compound emulsion method.The rotating speed of outer water and the concentration of outer water stablizer were controlled when microspherulite diameter can be by the viscosity of colostrum emulsion, emulsion, and magnetic content can be controlled by the concentration of interior aqueous phase solute and the ratio of interior water volume and oil phase volume.This magnetic microsphere can be used as the carrier of various enzymes, antibody, targeted drug, is widely used in fields such as cellular segregation, clinical diagnosis, target medicine carrier, immobilized enzyme, affine separation.Characteristics such as the present invention has that method is simple, good reproducibility, raw material are easy to get, cost is low, microspherulite diameter is controlled, microballoon magnetic uniform content, microballoon magnetic content are controlled.
The purpose of this invention is to provide a kind of method of quick, efficient, magnetic content controllable preparation magnetic macromolecular microsphere, this method is different from all methods of having reported fully.This kind method can monomer or polymer prepare magnetic macromolecular microsphere as raw material.
Description of drawings:
Magnetic macromolecular microsphere suspended state in water when no magnetic field of Fig. 1 embodiment 1 preparation.
Separating effect behind the placement 5min clock of magnetic macromolecular microsphere in the magnetic field of 2000T of Fig. 2 embodiment 1 preparation.
The optical microphotograph picture of the magnetic macromolecular microsphere of Fig. 3 embodiment 1 preparation.
The scanning electron microscopy sheet of the magnetic macromolecular microsphere of Fig. 4 embodiment 1 preparation.
The grain size distribution curve of the magnetic macromolecular microsphere of Fig. 5 embodiment 1 preparation.
The scanning electron microscopy sheet of the magnetic macromolecular microsphere of Fig. 6 embodiment 2 preparations.
The scanning electron microscopy sheet of the magnetic macromolecular microsphere of Fig. 7 embodiment 3 preparations.
The scanning electron microscopy sheet of the magnetic macromolecular microsphere of Fig. 8 embodiment 4 preparations.
The scanning electron microscopy sheet of the magnetic macromolecular microsphere of Fig. 9 embodiment 5 preparations.
Specific embodiments
1, when using polymer as raw material, its preparation process is as follows:
(1) with polymer, surfactant dissolves in organic solvent, be prepared into oil phase O;
(2) with metal ion salt solution W
1O mixes with oil phase, uses one or both method couplings in sonioation method and the homogenizing emulsifying method, makes W
1The colostrum emulsion that/O type is stable;
(3) with W
1/ O type colostrum emulsion joins a certain amount of outer water W
2In (moisture and stablizer), use the method for homogenizing emulsifying method or magnetic agitation, be prepared into W
1/ O/W
2The type emulsion;
(4) a certain amount of organic bases or mineral alkali are joined outer water W
2In, stirring, alkali is diffused into interior aqueous phase, generates magnetic-particle with the molysite reaction;
(5) with the organic solvent evaporation in the emulsion emulsion droplet, the emulsion emulsion droplet solidifies, thereby generates magnetic macromolecular microsphere;
(6) add the magnetic field separation magnetic microsphere, and also dry with diluted acid, ethanol and deionized water repetitive scrubbing, obtain finished product---magnetic macromolecular microsphere.
2, when using monomer as raw material, its preparation process is as follows:
(1) monomer, linking agent, tensio-active agent and initiator are dissolved in the organic solvent, are prepared into oil phase O;
(2) with metal ion salt solution W
1O mixes with oil phase, uses one or both method couplings in sonioation method and the homogenizing emulsifying method, makes W
1The colostrum emulsion that/O type is stable;
(3) with W
1/ O type colostrum emulsion joins a certain amount of outer water W
2In (moisture and stablizer), use the method for homogenizing emulsifying method or magnetic agitation, be prepared into W
1/ O/W
2The type emulsion;
(4) heat up, make monomer and linking agent copolymerization;
(5) a certain amount of organic bases or mineral alkali are joined outer water W
2In, stirring, alkali is diffused into interior aqueous phase, generates magnetic-particle with the molysite reaction;
(6) continue polymerization, and with the organic solvent evaporation in the emulsion emulsion droplet, the emulsion emulsion droplet solidifies, thereby generate magnetic macromolecular microsphere;
(7) add the magnetic field separation magnetic microsphere, and also dry with diluted acid, ethanol and deionized water repetitive scrubbing, obtain finished product---magnetic macromolecular microsphere.
In the existing report method, suspension polymerization is at first to prepare magnetic-particle, refabrication magnetic--high molecular composite microsphere; Interface sedimentation and activation swelling method are at first to prepare the nano level microballoon, at microsphere surface or the inner magnetic-particle that generates, prepare magnetic macromolecular microsphere as the seed microballoon at last again; The reverse microemulsion method is to adopt w/o type (water-in-oil-type) microemulsion, only is suitable for hydrophilic monomer or polymkeric substance.And the compound emulsion method that the present invention uses is different from existing all methods, it is characterized in that the limit generates magnetic-particle, and the limit makes emulsion solidify balling-up, thereby magnetic-particle is embedded in the polymer microsphere, and a step is prepared magnetic macromolecular microsphere.
Present method is used compound emulsion method, it is characterized in that preparing with compound emulsion method earlier the emulsion emulsion of inner embedding iron salt solutions, and then adds organic bases or mineral alkali makes molysite be converted into magnetic-particle, the emulsion emulsion droplet is solidified again, and prepares magnetic macromolecular microsphere.Present method can be controlled magnetic content and reach the requirement of high embedding amount.
Embodiment 1:
Get the PSt of 0.30g and the Span85 of 0.06g (Witconol AL 69-66), be dissolved in the 6.50mL toluene, form oil phase O.With W
1(0.40mL concentration is the FeCl of 1.00mol/L
3The aqueous solution and 0.20ml concentration are the FeSO of 1.00mol/L
4The aqueous solution) join among the oil phase O, stir 2min with the emulsification clarifixator, rotating speed is 10000rpm, forms stable W
1/ O type colostrum emulsion.With the W that has prepared
1/ O type colostrum emulsion is slowly poured the outer water W of 250mL into
2(H
2O is 250.0g, and PVA-217 is 1.0g) the middle stirring, rotating speed is 400rpm, forms W
1/ O/W
2Type emulsion emulsion, outside then aqueous phase adds the triethylamine of 50mL, and 2hr is stirred in nitrogen protection down, is warming up to 45 ℃ of uncovered stirring 6hr then, is cooled to stirring at room 18br more naturally toluene is volatilized fully.Separation in externally-applied magnetic field, washing, vacuum-drying at last promptly gets product.During no externally-applied magnetic field, product is scattered in the water, microballoon can suspend in water, as shown in Figure 1; When externally-applied magnetic field is 0.2T, microballoon can with the water sharp separation, as shown in Figure 2.The optical photograph of magnetic macromolecular microsphere as shown in Figure 3, the scanning electron microscope picture is as shown in Figure 4.The size distribution of microballoon as shown in Figure 5.Magnetic-particle is embedded in the polymer microsphere well, does not have leakage phenomenon.
Embodiment 2:
Get the PSt of 0.30g and the Arace183 of 0.06g (sorbitan sesquioleate), be dissolved in the 6.00mL methylene dichloride, form oil phase O.With W
1(0.30mL concentration is the FeCl of 0.80mol/L
3The aqueous solution and 0.3ml concentration are the FeCl of 0.80mol/L
2The aqueous solution) join among the oil phase O, use supersound method emulsification, emulsification power is 200W, and the time is 2min, forms stable W
1/ O type colostrum emulsion.With the W that has prepared
1/ O type colostrum emulsion is slowly poured the outer water W of 350mL into
2(H
2O is 350.0g, and PVA-217 is 1.75g) the middle stirring, rotating speed is 400rpm, forms W
1/ O/W
2Type emulsion emulsion, outwards aqueous phase adding 25mL concentration is the potassium hydroxide solution of 2mol/L then, 2hr is stirred in nitrogen protection down, is cooled to the uncovered stirring of room temperature 24hr then naturally methylene dichloride is volatilized fully.Separation in externally-applied magnetic field, washing, vacuum-drying at last promptly gets product.The scanning electron microscope picture of magnetic macromolecular microsphere as shown in Figure 6.
Embodiment 3:
Get the PSt of 0.30g and the Span85 of 0.08g (Witconol AL 69-66), be dissolved in 5.50mL toluene and the 1.00mL methylene dichloride, form oil phase O.With W
1(0.30mL concentration is the FeCl of 0.50mol/L
3The aqueous solution and 0.30ml concentration are the FeCl of 0.50mol/L
2The aqueous solution) join among the oil phase O, stir 2min with the emulsification clarifixator, rotating speed is 9000rpm, forms stable W
1/ O type colostrum emulsion.With the W that has prepared
1/ O type colostrum emulsion is slowly poured the outer water W of 300mL into
2(H
2O is 300.0g, and PVA-217 is 3.0g) in, stirring with homogeneous emulsifying machine, rotating speed is 600rpm, forms W
1/ O/W
2Type emulsion emulsion is used mechanical stirring then, and rotating speed is 400rpm, and outside then aqueous phase adds the triethylamine of 50mL, and 2hr is stirred in nitrogen protection down, is warming up to 45 ℃ of uncovered stirring 6hr then, and decompression is volatilized toluene and methylene dichloride fully again.Separation in externally-applied magnetic field, washing, vacuum-drying at last promptly gets product.The scanning electron microscope picture of magnetic macromolecular microsphere as shown in Figure 7.
Embodiment 4:
Get the BPO of DVB, 0.005g of St, 0.05g of 0.25g and the Span85 of 0.04g, be dissolved in the toluene of 5.0mL, form oil phase O.With W
1(0.10mL concentration is the FeCl of 0.50mol/L
3The aqueous solution and 0.20mL concentration are the FeCl of 0.50mol/L
2The aqueous solution) join among the oil phase O, stir 1min with the emulsification clarifixator earlier, rotating speed is 9000rpm, uses supersound method emulsification again, and emulsification power is 250W, and the time is 1min, forms stable W
1/ O type colostrum emulsion.With the W that has prepared
1/ O type colostrum emulsion is slowly poured the outer water W of 300mL into
2(H
2O is 300.0g, and PVA-217 is 1.50g) the middle stirring, form W
1/ O/W
2Type emulsion emulsion, rotating speed are 500rpm, with the emulsion emulsion be warming up under the nitrogen protection 75 ℃ make the monomer polymerization certain hour after, in the emulsion emulsion, add 40mL ammoniacal liquor, continue to be cooled to stirring at room 24hr behind the polymerization 8hr and make the toluene volatilization.Separation in externally-applied magnetic field, washing, vacuum-drying at last promptly gets product.The scanning electron microscope picture of magnetic macromolecular microsphere as shown in Figure 8.
Embodiment 5:
Get the BPO of DVB, 0.006g of MMA, 0.05g of St, 0.05g of 0.25g and the Span80 (Witconol AL 69-66) of 0.04g, be dissolved in the toluene and 0.50mL ethyl acetate of 5.50mL, form oil phase O.With W
1(0.15mL concentration is the FeCl of 0.60mol/L
3The aqueous solution and 0.30mL concentration are the FeCl of 0.60mol/L
2The aqueous solution) join among the oil phase O, stir 2min with the emulsification clarifixator, rotating speed is 10000rpm, forms stable W
1/ O type colostrum emulsion.With the W that has prepared
1/ O type colostrum emulsion is slowly poured the outer water W of 250mL into
2(H
2O is 250.0g, and PVA-217 is 2.5g) the middle stirring, form W
1/ O/W
2Type emulsion emulsion; rotating speed is 500rpm; make monomer polymerization after for some time being warming up to 75 ℃ under the nitrogen protection emulsion emulsion, adding 20mL concentration in the emulsion emulsion is the sodium hydroxide solution of 2mol/L, continues to be cooled to the room temperature decompression behind the polymerization 8hr toluene and ethyl acetate are volatilized fully.Separation in externally-applied magnetic field, washing, vacuum-drying at last promptly gets product.The scanning electron microscope picture of magnetic macromolecular microsphere as shown in Figure 9.
Reference:
1、J.C.Daniel，J.L.Schuppiser，M.Tricot，US?Patent?4,358,388(1982)
2, Li Xiaohong, Ding Xiaobin, Sun Zonghua, functional polymer journal, 1,73 (1995)
3, official's moon is put down Liu Huizhou, An Zhentao, Ke Jiajun, old family a large bell Chinese patent 98124516.1 (1998)
4、J.Ugelstad，P.Stenstad，L.Kilaas，Blood?Puri.，11，349(1993)
5、J.Ugelstad，P.C.Mork，R.Schmid，T.Ellingsen，A.Berg，Polymer?International，30，157(1993)
6、K.Furusawa，K.Nagashima，C.Anzai，Kobunshi?Eonbunshu，50，337(1993)
7、S.James，WO?Patent，96/37131(1996)
8, Wang Lei, Deng Yonghua, A Deer Hammett Euler Sa, wide Chinese patent 01126181.1 (2001) of mansion longevity
9, Deng Yonghui, Wang Lei, Yang Wuli, wide, the high chemical journal of ElaissariAbdelhamid of mansion longevity, 24 (5), 920, (2003)
Claims (13)
1. a method for preparing magnetic macromolecular microsphere is characterized in that using polymer as raw material, and preparation process is as follows:
(1) with polymer, surfactant dissolves in organic solvent, be prepared into oil phase O;
(2) with iron salt solutions W
1O mixes with oil phase, uses sonioation method and homogenizing emulsifying method
In one or both method couplings, make W
1The colostrum emulsion that/O type is stable;
(3) with W
1/ O colostrum emulsion joins the outer water W of a certain amount of moisture and stablizer
2In,
Use the method for homogenizing emulsifying method or magnetic agitation, be prepared into W
1/ O/W
2The type emulsion;
(4) a certain amount of organic bases or mineral alkali are joined outer water W
2In, stirring, alkali is diffused into interior aqueous phase, generates magnetic-particle with the molysite reaction;
(5) with the organic solvent evaporation in the emulsion emulsion droplet, the emulsion emulsion droplet solidifies, thereby generates magnetic macromolecular microsphere;
(6) add the magnetic field separation magnetic microsphere, and also dry with diluted acid, ethanol and deionized water repetitive scrubbing, obtain finished product---magnetic macromolecular microsphere.
2. a method for preparing magnetic macromolecular microsphere is characterized in that using monomer as raw material, and preparation process is as follows:
(1) monomer, linking agent, tensio-active agent and initiator are dissolved in the organic solvent, are prepared into oil phase O;
(2) with iron salt solutions W
1O mixes with oil phase, uses one or both method couplings in sonioation method and the homogenizing emulsifying method, makes W
1The colostrum emulsion that/O type is stable;
(3) with W
1/ O colostrum emulsion joins the outer water W of a certain amount of moisture and stablizer
2In,
Use the method for homogenizing emulsifying method or magnetic agitation, be prepared into W
1/ O/W
2The type emulsion;
(4) heat up, make monomer and linking agent copolymerization;
(5) a certain amount of organic bases or mineral alkali are joined outer water W
2In, stirring, alkali is diffused into interior aqueous phase, generates magnetic-particle with the molysite reaction;
(6) continue polymerization, and with the organic solvent evaporation in the emulsion emulsion droplet, the emulsion emulsion droplet solidifies, thereby generate magnetic macromolecular microsphere;
(7) add the magnetic field separation magnetic microsphere, and also dry with diluted acid, ethanol and deionized water repetitive scrubbing, obtain finished product---magnetic macromolecular microsphere.
3. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 is characterized in that polymer is the multipolymer of one or more hydrophobic polymers and hydrophobic monomer and hydrophilic monomer copolymerization generation.
4. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 is characterized in that polymer is a polystyrene.
5. the method for preparing magnetic macromolecular microsphere as claimed in claim 2 is characterized in that monomer is the mixture of one or more hydrophobic monomers and hydrophobic monomer and hydrophilic monomer.
6. the method for preparing magnetic macromolecular microsphere as claimed in claim 2 is characterized in that monomer is a vinylbenzene.
7. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 is characterized in that organic solvent is selected from one or more in ethyl acetate, toluene and the methylene dichloride.
8. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2 is characterized in that molysite is the salts solution that can generate magnetic substance with basic solution by coprecipitation reaction.
9. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2 is characterized in that molysite is iron(ic) chloride or ferrous sulfate.
10. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2 is characterized in that magnetic-particle is γ-Fe
2O
3Perhaps Fe
3O
4
11. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2, the size that it is characterized in that polymer microsphere are 50nm～800 μ m.
12. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2 is characterized in that making the method for organic solvent evaporation to be selected from normal pressure intensification volatilization method, normal pressure and temperature volatilization method, decompression extraction process or the vacuum extraction method one or several.
13. the method for preparing magnetic macromolecular microsphere as claimed in claim 1 or 2, it is characterized in that magnetic-particle comprises ferromagnetic particle and supperparamagnetic particles, the quality control of the alkali that adds in concentration that its magnetic property can be by each metal ion species of aqueous phase in regulating and the emulsion.
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| CN103374143B (en) * | 2012-04-28 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of super large pore polymer microsphere and preparation method thereof |
| CN103387625B (en) * | 2012-05-07 | 2015-09-02 | 中国石油化工股份有限公司 | The preparation method of polystyrene hollow microsphere and application thereof |
| CN103113515B (en) * | 2013-02-28 | 2015-08-05 | 中国科学院长春应用化学研究所 | A kind of magnetic porous polymer beads and preparation method thereof |
| CN104558353A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Method for preparing magnetic polymer microspheres by multiple emulsion method |
| EP3144058A1 (en) * | 2015-09-16 | 2017-03-22 | Calyxia | Method for preparing microcapsules by double emulsion |
| CN107164090A (en) * | 2017-05-31 | 2017-09-15 | 东南大学 | A kind of cigarette perfume microcapsule and preparation method |
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| 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 |
| CN1328064A (en) * | 2001-07-16 | 2001-12-26 | 复旦大学 | nm Microspheres of magnetic polymer synthesized by one-step method and its preparing process |
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2005
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|---|---|---|---|---|
| US4358388A (en) * | 1980-04-18 | 1982-11-09 | Rhone Poulenc Industries | Magnetic polymer latex and preparation process |
| 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 |
| CN1328064A (en) * | 2001-07-16 | 2001-12-26 | 复旦大学 | nm Microspheres of magnetic polymer synthesized by one-step method and its preparing process |
Non-Patent Citations (1)
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