CN100425627C - Preparation process of magnetic partical/polymer/silicon dioxide structure magnetic microball - Google Patents
Preparation process of magnetic partical/polymer/silicon dioxide structure magnetic microball Download PDFInfo
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- CN100425627C CN100425627C CNB2007100552045A CN200710055204A CN100425627C CN 100425627 C CN100425627 C CN 100425627C CN B2007100552045 A CNB2007100552045 A CN B2007100552045A CN 200710055204 A CN200710055204 A CN 200710055204A CN 100425627 C CN100425627 C CN 100425627C
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Abstract
The present invention is preparation process of magnetic particle/polymer/silica magnetic microsphere and belongs to the field of magnetic material technology. The technological process includes the following steps: 1. dispersing nanometer hydrophobic magnetic particle in solvent comprising silane reagent and olefin monomer to form oil phase, dissolving surfactant in water to form water phase, mixing to form oil-in-water suspension, adding initiator to initiate polymerization to obtain magnetic microsphere with polymer in the surface; and 2. dispersing the magnetic microsphere with polymer in mixed solvent comprising alcohol, water and ammonia water and hydrolyzing condensation of ethyl silicate to grow silica layer. The present invention has simple silica layer growth process and excellent controllability, and the prepared magnetic composition particle has excellent biocompatibility and high chemical stability and may be further functionated.
Description
Technical field
The invention belongs to field of magnetic material, the preparation method of particularly a kind of magnetic particle/polymkeric substance/silicon dioxide structure magnetic microsphere.
Background technology:
The superparamagnetism microballoon has a wide range of applications in the fields such as orientation conveying of the isolation and purification of biotechnology and biomedicine field such as cell, albumen, DNA and RNA, nuclear magnetic resonance radiography, medicine.These application requiring magnetic microspheres have stronger magnetic, good chemical stability, excellent biological compatibility and distribute than homogeneous particle diameter.For satisfying above-mentioned requirements, the general method that coats protective layer on the magnetic particle surface that adopts prepares magnetic microsphere.The method of prior art for preparing magnetic microsphere mainly contains biomolecules entrapping method, polymer overmold method and coated with silica method.The magnetic microsphere monodispersity of biological entrapping method preparation is poor, loosely organized, chemical stability is relatively poor; The magnetic microsphere biocompatibility of polymer overmold preparation is relatively poor, colloidal stability is bad; And the magnetic microsphere good biocompatibility of coated with silica method preparation, but magnetic substance content is low and difficult control, size distribution broad.
The prior art that is close most with the present invention is one piece of document, and exercise question is " Development of HighMagnetization Fe
3O
4/ Polystyrene/Silica Nanospheres via CombinedMiniemulsion/Emulsion Polymerization " (J.Am.Chem.Soc., 2006,128,15582-15583).Announced a kind of Fe in the document
3O
4The making method of/polystyrene/silica dioxide magnetic microsphere, its making method has the following steps: the first step, prepare the hydrophobic magnetic nanoparticle with known coprecipitation method, and it is dispersed in the stable flowing molten iron body of formation in the heptane, with flowing molten iron body and the aqueous solution that is dissolved with tensio-active agent, its dispersion is obtained oil-in-water miniemulsion then by ultrasonic; In second step, vinylbenzene is formed the vinylbenzene oil droplet by emulsifier unit (membrane emulsification equipment); The 3rd step, miniemulsion and the vinylbenzene oil droplet that obtains in first and second step mixed, initiated polymerization prepares hydrophobic Fe
3O
4/ polystyrene magnetic microsphere; In the 4th step, use tensio-active agent (polyoxyethylene20 sorbitan monolaurate) with hydrophobic Fe
3O
4/ polystyrene magnetic microsphere is dispersed in the water, successively adds propyl alcohol and tetraethoxy with Fe
3O
4/ polystyrene magnetic microsphere swelling adds the ammonia-catalyzed growthing silica and obtains Fe
3O
4/ polystyrene/silica dioxide magnetic microsphere.
Background technology adopts a kind of mini-emulsion polymerization/method of emulsion polymerization of having mixed to prepare Fe
3O
4/ polystyrene/silica dioxide magnetic microsphere.But, the Fe that in preparation process, adopts the miniemulsion method to prepare
3O
4/ polystyrene magnetic microsphere is hydrophobic, can not be at the hydrophilic silicon-dioxide of its surperficial direct growth.Therefore, in preparation process at first with tensio-active agent with Fe
3O
4/ polystyrene magnetic microsphere is dispersed in the water, adds propyl alcohol and tetraethoxy then with Fe
3O
4/ polystyrene magnetic microsphere swelling, tetraethoxy is at Fe under the ammonia-catalyzed effect
3O
4/ polystyrene magnetic microsphere surface growth silicon-dioxide.Preparation method's complex steps of background technology, complicated operation, and in the growthing silica process, introduce a large amount of tensio-active agents, and stable magnetic microsphere biocompatibility difference of tensio-active agent and tensio-active agent are at SiO
2The surface is difficult for removing, and is unfavorable for further biologic applications.
Summary of the invention
At the deficiency of existing preparation magnetic microsphere technology, the present invention proposes the magnetic microsphere preparation method of a kind of magnetic particle/polymkeric substance/silicon dioxide structure.This preparation method is simple, introduces silane reagent and make coupling agent in preparation process, prepares the high molecular polymer magnetic microsphere of surface silanol group functionalization, and the silicon hydroxyl that utilizes high molecular polymer magnetic microsphere surface is directly at its surface growth silicon-dioxide.The magnetic microsphere that this preparation method obtains has that superparamagnetism, stronger foreign field responding ability, particle diameter are controlled, silicon dioxide layer controllable thickness and the narrower characteristics of size distribution, and magnetic composite microsphere has excellent biological compatibility and chemical stability simultaneously.
The preparation method of magnetic particle/polymkeric substance of the present invention/silicon dioxide structure magnetic microsphere has that high molecular polymer coats, the technological process of coated with silica.
Said high molecular polymer cladding process is a preparation hydrophobic magnetic nanoparticle, and it is dispersed in the solution that silane reagent and vinyl monomer form forms oil phase; With the water-soluble formation water of tensio-active agent, the weight ratio content of tensio-active agent in water is 0.2%～5%; Stir or ultrasonicly oil phase is dispersed in water forms oil-in-water suspension or fine suspension; Under 50～90 ℃, add the initiator initiated polymerization, reacted 6～12 hours, obtain the high molecular polymer magnetic microsphere of surface silanol group functionalization; Wherein, the volume ratio of silane reagent and vinyl monomer is 1: 50～1: 1, and hydrophobic magnetic nanoparticle concentration in the mixing solutions of silane reagent and vinyl monomer is 0.3g/ml～1.8g/ml;
Said coated with silica technology, be that the high molecular polymer magnetic microsphere is dispersed in the mixing solutions of alcohol, water and ammoniacal liquor, divide 1～10 time and add tetraethoxy, each joining day is spaced apart 3～6 hours, after tetraethoxy all adds, continue reaction 5～15 hours again, prepare the magnetic microsphere of magnetic particle/polymkeric substance/silicon dioxide structure; The concentration of high molecular polymer magnetic microsphere in mixing solutions is 0.1～5mg/ml, and the concentration of tetraethoxy in mixing solutions is 0.1～85g/L; The volume ratio of alcohol and water is 5: 1～50: 1; The volumetric molar concentration of ammoniacal liquor is 0.25～1.2mol/L.
In the preparation method of magnetic particle/polymkeric substance of the present invention/silicon dioxide structure magnetic microsphere, said silane reagent is 1～3 kind in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, allyltrimethoxysilanis, 3-(methacryloxypropyl) propyl trimethoxy silicane; Said vinyl monomer is 1～3 kind in vinylbenzene, methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, vinylcarbinol, the acrylamide; Said tensio-active agent is 1～2 kind in sodium lauryl sulphate, hexadecanol, polyvinylpyrrolidone, methylene blue, the cetyl trimethylammonium bromide; Said initiator is 1～2 kind in Potassium Persulphate, ammonium persulphate, benzoyl peroxide, the Diisopropyl azodicarboxylate.
In high molecular polymer coating process, be preparation hydrophobic magnetic nanoparticle and it is dispersed in the solution that silane reagent and vinyl monomer form forms stable oil phase dispersive magnetic fluid.Concrete is under 50～90 ℃, is 1: 2 Fe with mol ratio
2+Or Co
2+Or Mn
2+And Fe
3+Or Co
3+Solution join fast in the ammonia soln, add C fast
8～C
22Stearic acid obtains the hydrophobic magnetic nanoparticle behind the stirring reaction, the particle diameter of hydrophobic magnetic nanoparticle is 5～15nm, is dispersed at last in the solution that silane reagent and vinyl monomer form and forms oil phase.
Control the content of hydrophobic magnetic nanoparticle in oil phase, can regulate and control the particle diameter of high molecular polymer magnetism of magnetic microsphere substances content and high molecular polymer magnetic microsphere.
In coated with silica technology, the high molecular polymer magnetic microsphere of surface silanol group functionalization is dispersed in the mixing solutions of alcohol, water and ammoniacal liquor, add tetraethoxy, be the close silicon effect that has utilized high molecular polymer magnetic microsphere surface silanol group, by hydrolyzing condensation of ethyl silicate growthing silica layer.
In the coated with silica process, tetraethoxy also can be to add in batches, is beneficial to control silica shell layer thickness.
As mentioned above, the present invention has set forth the preparation method that a kind of preparation has magnetic particle/polymkeric substance/silicon dioxide structure magnetic microsphere, this preparation method has following characteristics: (1) preparation method is simple, coats by high molecular polymer---and coated with silica two step process are realized; (2) introduce silane reagent in the preparation process, make the silicon dioxide layer grows process simple; (3) in preparation process, the regulation and control reaction conditions can be realized the controlled of magnetic substance content, microspherulite diameter, high molecular polymer kernel particle diameter and silica shell; (4) Zhi Bei magnetic compound particles has excellent biological compatibility and chemical stability, and is easy to further functionalization such as amino, carboxyl, sulfydryl.
Embodiment
Embodiment 1: the preparation of hydrophobic magnetic nanoparticle (1)
To the Fe of 100ml through adding 0.046mol in the water of letting nitrogen in and deoxidizing
3+Fe with 0.023mol
2+Obtain mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the reaction flask of 1L, the mass percent concentration that adds 20ml successively is 25% strong aqua and 1.33g 10 hendecenoic acid, rapidly to wherein pouring above-mentioned molysite mixing solutions into, reacts 1h down at 50 ℃ under vigorous stirring.After reaction finishes, with hydrochloric acid reaction soln is transferred to acidity, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets hydrophobic Fe 3～5 times with the high purity water cleaning
3O
4Nanoparticle.
With Fe
3+And Fe
2+Replace to Co respectively
3+And Co
2+, can obtain hydrophobic Co
3O
4Nanoparticle.
Embodiment 2: the preparation of hydrophobic magnetic nanoparticle (2)
To the Fe of 100ml through adding 0.046mol in the water of letting nitrogen in and deoxidizing
3+Fe with 0.023mol
2+Obtain mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 20ml successively is 25～28% strong aqua and 5.52g myristic acid, rapidly to wherein pouring above-mentioned molysite mixing solutions into, reacts 1h down at 80 ℃ under vigorous stirring.Aerating oxygen 2h in reaction soln then.After reaction finishes, with hydrochloric acid just reaction soln transfer to acidity, from reaction soln, isolate red solid with the permanent magnet of 0.1T, the gained solid promptly gets hydrophobic γ-Fe 3～5 times with the high purity water cleaning
2O
3Nanoparticle
Embodiment 3: the preparation of hydrophobic magnetic nanoparticle (3)
To the Fe of 100ml through adding 0.046mol in the water of letting nitrogen in and deoxidizing
3+With 0.023mol Co
2+Obtain mixing solutions.Get 400ml water letting nitrogen in and deoxidizing in the reaction flask of 1L, the mass percent concentration that adds 20ml successively is 25% strong aqua and 10.8g oleic acid, rapidly to wherein pouring above-mentioned mixing solutions into, reacts 1h down at 90 ℃ under vigorous stirring.After reaction finishes, with hydrochloric acid reaction soln is transferred to acidity, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets CoFe 3～5 times with the high purity water cleaning
2O
4The dewatering nano particle.
With Co
2+Replace to Mn
2+, can obtain hydrophobic MnFe
2O
4Nanoparticle.
Embodiment 4: the preparation of high molecular polymer magnetic microsphere (1)
With the hydrophobic Fe among the embodiment 1
3O
4Magnetic nano-particle 1g is scattered in the vinyltriethoxysilane mixing solutions of 3ml methyl methacrylate and 0.06ml and forms oil phase; Get in the water that 1.875g sodium lauryl sulphate and 5.625g hexadecanol be dissolved in 150ml and form water.Respectively oil phase, water are changed in the reactor, form oil-in-water emulsion by ultra-sonic dispersion.Be warming up to 50 ℃, add 0.1g Potassium Persulphate and 0.2g ammonium persulphate, under 350rpm, react 6h.Reaction promptly obtains coating Fe after finishing
3O
4The high molecular polymer magnetic microsphere.
Also methyl methacrylate can be replaced to any of following vinyl monomer: vinylbenzene, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, vinylcarbinol, acrylamide; Also vinyltriethoxysilane can be replaced to any of following silane reagent: vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, allyltrimethoxysilanis, 3-(methacryloxypropyl) propyl trimethoxy silicane.
Embodiment 5: the preparation of high molecular polymer magnetic microsphere (2)
With the hydrophobic γ-Fe among the embodiment 2
2O
3Magnetic nano-particle 3g is scattered in the mixing solutions of 2ml vinylbenzene, 0.5ml butyl methacrylate, 0.5ml vinylcarbinol, 0.3ml allyltrimethoxysilanis, adds benzoyl peroxide 0.1g, forms oil phase; Get in the water that 1.5g polyvinylpyrrolidone and 0.05g methylene blue be dissolved in 150ml and form water.Respectively oil phase, water are changed in the reactor, form oil-in-water emulsion, be warming up to 70 ℃, add the Potassium Persulphate of 0.3g, under 350rpm stirs, react 9h by ultra-sonic dispersion.Reaction promptly obtains coating γ-Fe after finishing
2O
3The high molecular polymer magnetic microsphere.
Allyltrimethoxysilanis can be replaced in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, 3-(methacryloxypropyl) propyl trimethoxy silicane any.
Embodiment 6: the preparation of high molecular polymer magnetic microsphere (3)
With the hydrophobic CoFe among the embodiment 3
2O
4Nanoparticle 5g is scattered in the mixing solutions of 0.5ml vinylbenzene, 0.5ml Propenoic acid, 2-methyl, isobutyl ester, 0.5ml acrylamide, 0.5ml vinyltrimethoxy silane, 0.5ml vinyl three (2-methoxy ethoxy) silane, 0.5ml 3-(methacryloxypropyl) propyl trimethoxy silicane, add the 0.5g Diisopropyl azodicarboxylate, form oil phase; Get in the water that the 0.3g cetyl trimethylammonium bromide is dissolved in 150ml and form water.Respectively oil phase, water are changed in the reactor, form oil-in-water emulsion, be warming up to 90 ℃, under 350rpm, react 12h by high-speed stirring.Reaction promptly obtains coating CoFe after finishing
2O
4The high molecular polymer magnetic microsphere.
Can be with hydrophobic CoFe
2O
4Nanoparticle replaces to hydrophobic MnFe
2O
4
Embodiment 7: coated with silica (1)
With the coating Fe among the embodiment 4
3O
4High molecular polymer magnetic microsphere 0.1g be scattered in 500ml ethanol, 10ml water and 10ml ammoniacal liquor (mass concentration 25%), add the 0.1ml tetraethoxy, under the stirring of 200rpm, react 15h, promptly obtain magnetic substance/high molecular polymer/silicone dioxide magnetic microsphere of median size 75nm, its silica shell mean thickness 6nm.
Embodiment 8: coated with silica (2)
With the coating γ-Fe among the embodiment 5
2O
3High molecular polymer magnetic microsphere 0.5g be scattered in ethanol, 50ml water and the 25ml ammoniacal liquor (mass concentration 25%) of 500ml, under the stirring of 200rpm, add tetraethoxy in batches, adjacent twice joining day be 3h at interval, each adding 0.5ml tetraethoxy, the tetraethoxy that adds 2.5ml altogether, when tetraethoxy all adds, continue magnetic substance/high molecular polymer/silicone dioxide magnetic microsphere that reaction 10h promptly obtains median size 310nm, its silica shell mean thickness 90nm.
Embodiment 9: coated with silica (3)
With the coating CoFe among the embodiment 6
2O
4High molecular polymer magnetic microsphere 2.5g be scattered in the ethanol, 100ml water of 500ml, add 50ml ammoniacal liquor (mass concentration 25%), under the stirring of 200rpm, add tetraethoxy in batches, adjacent twice joining day be 5h at interval, each adding 5ml tetraethoxy, the tetraethoxy that adds 45ml altogether, when tetraethoxy all adds, continue magnetic substance/high molecular polymer/silicone dioxide magnetic microsphere that reaction 5h promptly obtains median size 1280nm, its silica shell mean thickness 450nm.
Claims (3)
1, the preparation method of a kind of magnetic particle/polymkeric substance/silicon dioxide structure magnetic microsphere is characterized in that, the technological process of high molecular polymer coating, coated with silica is arranged;
Said high molecular polymer cladding process is a preparation hydrophobic magnetic nanoparticle, and it is dispersed in the solution that silane reagent and vinyl monomer form forms oil phase; With the water-soluble formation water of tensio-active agent, the weight ratio content of tensio-active agent in water is 0.2%～5%; Stir or ultrasonicly oil phase is dispersed in water forms oil-in-water suspension or fine suspension; Under 50～90 ℃, add the initiator initiated polymerization, reacted 6～12 hours, obtain the high molecular polymer magnetic microsphere of surface silanol group functionalization; Wherein, the volume ratio of silane reagent and vinyl monomer is 1: 50～1: 1, and hydrophobic magnetic nanoparticle concentration in the mixing solutions of silane reagent and vinyl monomer is 0.3g/ml～1.8g/ml; Said silane reagent is 1～3 kind in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, allyltrimethoxysilanis, 3-(methacryloxypropyl) propyl trimethoxy silicane; Said vinyl monomer is 1～3 kind in vinylbenzene, methyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, vinylcarbinol, the acrylamide;
Said coated with silica technology, be that the high molecular polymer magnetic microsphere is dispersed in the mixing solutions of alcohol, water and ammoniacal liquor, divide 1～10 time and add tetraethoxy, each joining day is spaced apart 3～6 hours, after tetraethoxy all adds, continue reaction 5～15 hours again, prepare the magnetic microsphere of magnetic particle/polymkeric substance/silicon dioxide structure; The concentration of high molecular polymer magnetic microsphere in mixing solutions is 0.1～5mg/ml, and the concentration of tetraethoxy in mixing solutions is 0.1～85g/L; The volume ratio of alcohol and water is 5: 1～50: 1; The volumetric molar concentration of ammoniacal liquor is 0.25～1.2mol/L.
2, according to the preparation method of the described a kind of magnetic particle/polymkeric substance of claim 1/silicon dioxide structure magnetic microsphere, it is characterized in that, said tensio-active agent is 1～2 kind in sodium lauryl sulphate, hexadecanol, polyvinylpyrrolidone, methylene blue, the cetyl trimethylammonium bromide; Said initiator is 1～2 kind in Potassium Persulphate, ammonium persulphate, benzoyl peroxide, the Diisopropyl azodicarboxylate.
3, according to the preparation method of claim 1 or 2 described a kind of magnetic particle/polymkeric substance/silicon dioxide structure magnetic microspheres, it is characterized in that, said preparation hydrophobic magnetic nanoparticle, and it is dispersed in the solution that silane reagent and vinyl monomer form forms stable oil phase, being under 50～90 ℃, is 1: 2 Fe with mol ratio
2+Or Co
2+Or Mn
2+And Fe
3+Or Co
3+Solution directly join in the ammonia soln, add C immediately
8～C
22Stearic acid, and stirring reaction 0.5～2 hour obtain the hydrophobic magnetic nanoparticle, and redispersion forms oil phase in the solution that silane reagent and vinyl monomer are formed.
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| CN113621113B (en) * | 2021-08-11 | 2022-07-26 | 天津博蕴纯化装备材料科技有限公司 | Alkenyl magnetic base ball and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236506A (en) * | 1998-02-23 | 1999-08-31 | Jsr Corp | Magnetic particle, production thereof, and carrier for nonspecific nucleic acid bonding |
| CN1451924A (en) * | 2002-04-18 | 2003-10-29 | 陈利君 | Method for making composite structure water heater internal chamber |
| CN1519866A (en) * | 2003-01-24 | 2004-08-11 | 中国科学院过程工程研究所 | Nano/micron microsphere with superparamagnetism and preparation method |
-
2007
- 2007-01-04 CN CNB2007100552045A patent/CN100425627C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236506A (en) * | 1998-02-23 | 1999-08-31 | Jsr Corp | Magnetic particle, production thereof, and carrier for nonspecific nucleic acid bonding |
| CN1451924A (en) * | 2002-04-18 | 2003-10-29 | 陈利君 | Method for making composite structure water heater internal chamber |
| CN1519866A (en) * | 2003-01-24 | 2004-08-11 | 中国科学院过程工程研究所 | Nano/micron microsphere with superparamagnetism and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 热敏性高分子包裹的磁性微球的性质及表征. 丁小斌，孙宗华，万国祥.《高分子学报》，第6期. 1999 |
| 热敏性高分子包裹的磁性微球的性质及表征. 丁小斌，孙宗华，万国祥.《高分子学报》，第6期. 1999 * |
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