CN101704980B - Polymethylacrylic acid magnetic composite microsphere and preparation method thereof - Google Patents
Polymethylacrylic acid magnetic composite microsphere and preparation method thereof Download PDFInfo
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- CN101704980B CN101704980B CN2009102189341A CN200910218934A CN101704980B CN 101704980 B CN101704980 B CN 101704980B CN 2009102189341 A CN2009102189341 A CN 2009102189341A CN 200910218934 A CN200910218934 A CN 200910218934A CN 101704980 B CN101704980 B CN 101704980B
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Abstract
The invention relates to a polymethylacrylic acid magnetic composite microsphere and a preparation method thereof. The microsphere is a composite microsphere with a core-shell structure, the polymer pore canal inside contains superparamagnetism nano particles to form multi-core part, and cross-linked methacrylic acid forms a shell layer to coat the core part from outside. The preparation method of the microsphere comprises: mixing surfactant and organic solvent under the protection of inert gas and stirring at 15-40 DEG C for 30-90min; adding methacrylic acid, cross-linking agent, magnetic nano particles and initiating agent and stirring at 20-40 DEG C for 10-60min; adding accelerant and stirring at 20-50 DEG C for 1.5-8h to obtain the microspheres. The polymethylacrylic acid magnetic composite microspheres have uniform particle diameter and controllable magnetism content, and the size of particle diameter can be controlled by controlling the reaction conditions; and the instrument and technique for preparing the polymethylacrylic acid magnetic composite microspheres are simple, the operation is convenient and the flexibility is high.
Description
Technical field
The present invention relates to technical field of macromolecules, relate in particular to a kind of polymethylacrylic acid magnetic composite microsphere and preparation method thereof.
Background technology
Magnetic macromolecular microsphere is meant the inorganic magnetic particle is combined a kind of complex microsphere that forms with organic polymer material, introduce and biologically active substance link coupled functional group by methods such as copolymerization, surface modifications, have superparamagnetism and make it can under the action of a magnetic field, finish repeatedly isolating operation, be widely used as magnetic carrier so contain the magnetic macromolecular microsphere of activity functional groups.Carry the magnetic macromolecular microsphere of carboxyl, can link polypeptide, protein and biological enzyme by carboxyl, also can modified connection other functional group, be a kind of ideal magnetic carrier.
People such as Yang Xu are with the Fe of coprecipitation method preparation
3O
4For the magnetic source, select acrylamide, N for use, N '-methylene-bisacrylamide and vinylformic acid are respectively as polymerization single polymerization monomer, linking agent and functional group monomer, and by inverse emulsion polymerization, the magnetic macromolecular microsphere of carboxyl is carried in the parcel preparation.Yuan Ding heavily waits the magnetic macromolecular microsphere of the employing compound emulsion method preparation of mentioning among the micron-sized P of people's synthetic (St/MAA) the magnetic macromolecular microsphere CN 1616524A, and the surface bond of mentioning among the CN 101139409A with methyl acrylic ester macromolecular compound coated ferroferric oxide magnetic particle kernel composition has the magnetic macromolecular microsphere of hydroxyl and amido.
More than the disclosed micron-sized magnetic macromolecular microsphere that contains activity functional groups have certain deficiency at aspects such as sphericity, monodispersity or magnetic content.
Summary of the invention
The object of the present invention is to provide a kind of sphericity, monodispersity good, the polymethylacrylic acid magnetic composite microsphere that magnetic content is controlled.
Another object of the present invention provides a kind of preparation method that can convenient preparation polymethylacrylic acid magnetic composite microsphere.
Technical solution of the present invention:
Polymethylacrylic acid magnetic composite microsphere, be a kind of complex microsphere of nucleocapsid structure, constitute that its special character is by the multinuclear core of inside and the shell of coating core, the multinuclear core of this microballoon inside is a magnetic nano-particle, and shell is crosslinked methacrylic acid.
Above-mentioned magnetic nano-particle is Fe
3O
4, γ-Fe
3O
4, NiFe
2O
4, CuFe
2O
4, iron, cobalt, nickel one or more.
The particle diameter of this polymethylacrylic acid magnetic composite microsphere is 0.5～200 μ m.
The magnetic content of this polymethylacrylic acid magnetic composite microsphere is 5%～50%.
The preparation method of above-mentioned polymethylacrylic acid magnetic composite microsphere, its special character is, may further comprise the steps:
1) tensio-active agent and organic solvent are mixed, feed rare gas element, 15～40 ℃ are stirred 30～90min;
2) under the protection of rare gas element, methacrylic acid, linking agent, magnetic nano-particle and initiator are mixed, join in the system of step 1), 20～40 ℃ are stirred 10～60min;
3) under the protection of rare gas element, to step 2) system in add promotor, 20～50 ℃ of stirring reaction 1.5～8h obtain polymethylacrylic acid magnetic composite microsphere.
Above-mentioned steps 3) reacting the polymethylacrylic acid magnetic composite microsphere that obtains also need clean with secondary water and ethanol.
Above-mentioned steps 1) tensio-active agent is Span40, Span80, Span60 or whiteruss; The step 1) organic solvent is toluene, hexanaphthene or tetrahydrobenzene;
Above-mentioned steps 2) linking agent is N, N '-methylene-bisacrylamide; Step 2) initiator is Potassium Persulphate or ammonium persulphate; Step 2) magnetic nano-particle is Fe
3O
4, γ-Fe
3O
4, NiFe
2O
4, CuFe
2O
4, iron, cobalt, nickel one or more.
Above-mentioned steps 3) promotor is Tetramethyl Ethylene Diamine or Tetrabutyl amonium bromide.
Above-mentioned rare gas element is helium, argon gas or nitrogen.
Advantage of the present invention is:
1, the polymethylacrylic acid magnetic composite microsphere particle diameter is even, and can be by the size of control reaction conditions control particle diameter.
2, polymethylacrylic acid magnetic composite microsphere magnetic content is controlled.
3, used plant and instrument and the technology of preparation polymethylacrylic acid magnetic composite microsphere is simple, easy to operate, and handiness is big.
Description of drawings
Fig. 1 is the polymethylacrylic acid magnetic composite microsphere structural representation, and wherein 1 is the multinuclear core, and 2 for coating the shell of core.
Fig. 2 (a) (b) is the polymethylacrylic acid magnetic composite microsphere stereoscan photograph of embodiment 1 preparation.
Fig. 3 (a) (b) is the polymethylacrylic acid magnetic composite microsphere stereoscan photograph of embodiment 2 preparations.
Fig. 4 is the polymethylacrylic acid magnetic composite microsphere saturation magnetization graphic representation of embodiment 1 preparation.
Fig. 5 is the polymethylacrylic acid magnetic composite microsphere saturation magnetization graphic representation of embodiment 2 preparations.
Specific embodiment
Polymethylacrylic acid magnetic composite microsphere, be the complex microsphere of nucleocapsid structure, constitute structural representation such as Fig. 1 by the multinuclear core 1 of inside and the shell 2 of coating core, the multinuclear core of this microballoon inside is a magnetic nano-particle, and this magnetic nano-particle is Fe
3O
4, γ-Fe
3O
4, NiFe
2O
4, CuFe
2O
4, iron, cobalt, nickel one or more, the shell of this microballoon is crosslinked methacrylic acid.The particle diameter of this microballoon is 0.1～200 μ m, and magnetic content is 5%～80%.
Below being polymethylacrylic acid magnetic composite microsphere preparation method's of the present invention specific embodiment, being used for further illustrating the present invention, is not to be used to limit protection scope of the present invention.
1) in the three-necked bottle of electric mixer is housed, 0.5g Span80 is dissolved in the 60ml toluene, under the condition of logical nitrogen protection, this system is reacted 30min while stirring, and temperature of reaction is 20 ℃;
2) under the condition of logical nitrogen protection, with 1ml methacrylic acid and 0.1g N, N '-methylene-bisacrylamide is dissolved in the 5ml secondary water, makes solution, this solution is joined in the system of step 1), adds 1ml (5～100mg/ml) Fe again
3O
4, and the 1ml Potassium Persulphate, this system is reacted 10min while stirring, and temperature of reaction is 30 ℃;
3) under the condition of logical nitrogen protection, to step 2) system in drip the 1ml Tetramethyl Ethylene Diamine, react 2h under 40 ℃ of conditions, after cleaning repeatedly with secondary water and ethanol, obtain polymethylacrylic acid magnetic composite microsphere.
Fig. 2 (a) is the polymethylacrylic acid magnetic composite microsphere stereoscan photograph of these embodiment 2 preparations (b), can see the polymethylacrylic acid magnetic composite microsphere uniform particle diameter of preparing with this method from photo, the about 50 μ m in this microballoon footpath.Fig. 4 is the polymethylacrylic acid magnetic composite microsphere saturation magnetization graphic representation of embodiment 1 preparation, and as can be seen from the figure this polymethylacrylic acid magnetic composite microsphere saturation magnetization is 3emu/g.
1) in the three-necked bottle of electric mixer is housed, 0.4g Span80 is dissolved in the 60ml toluene, under the condition of logical nitrogen protection, this system is reacted 30min while stirring, and temperature of reaction is 20 ℃;
2) under the condition of logical nitrogen protection, with 1ml methacrylic acid and 0.15g N, N '-methylene-bisacrylamide is dissolved in the 5ml secondary water, makes solution, this solution is joined in the system of step 1), adds 1ml (5～100mg/ml) Fe again
3O
4, and the 1ml Potassium Persulphate, this system is reacted 30min while stirring, and temperature of reaction is 20 ℃;
3) under the condition of logical nitrogen protection, to step 2) system in drip the 1ml Tetrabutyl amonium bromide, react 3h under 40 ℃ of conditions, after cleaning repeatedly with secondary water and ethanol, obtain polymethylacrylic acid magnetic composite microsphere.
Fig. 3 (a) is the polymethylacrylic acid magnetic composite microsphere stereoscan photograph of these embodiment 2 preparations (b), can see the polymethylacrylic acid magnetic composite microsphere uniform particle diameter of preparing with this method from photo, the about 10 μ m in this microballoon footpath.Fig. 5 is the polymethylacrylic acid magnetic composite microsphere saturation magnetization graphic representation of embodiment 2 preparations, and as can be seen from the figure this polymethylacrylic acid magnetic composite microsphere saturation magnetization is 18emu/g.
Claims (5)
1. the preparation method of a polymethylacrylic acid magnetic composite microsphere is characterized in that, this method may further comprise the steps:
1) tensio-active agent and organic solvent are mixed, feed rare gas element, 15～40 ℃ are stirred 30～90min;
2) under the protection of rare gas element, methacrylic acid, linking agent, magnetic nano-particle and initiator are mixed, join in the system of step 1), 20～40 ℃ are stirred 10～60min;
3) under the protection of rare gas element, to step 2) system in add promotor, 20～50 ℃ of stirring reaction 1.5～8h obtain polymethylacrylic acid magnetic composite microsphere; Described promotor is Tetramethyl Ethylene Diamine or Tetrabutyl amonium bromide.
2. preparation method according to claim 1 is characterized in that: the polymethylacrylic acid magnetic composite microsphere that the step 3) reaction obtains also need clean with secondary water and ethanol.
3. preparation method according to claim 1 and 2 is characterized in that: the step 1) tensio-active agent is Span40, Span80, Span60 or whiteruss; The step 1) organic solvent is toluene, hexanaphthene or tetrahydrobenzene.
4. preparation method according to claim 3 is characterized in that: step 2) linking agent is N, N '-methylene-bisacrylamide; Step 2) initiator is Potassium Persulphate or ammonium persulphate; Step 2) magnetic nano-particle is Fe
3O
4, γ-Fe
3O
4, NiFe
2O
4, CuFe
2O
4, iron, cobalt, nickel one or more.
5. preparation method according to claim 4 is characterized in that: described rare gas element is helium, argon gas or nitrogen.
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| CN117662100B (en) * | 2024-02-02 | 2024-04-26 | 中国石油大学(华东) | Fractured reservoir plugging control system and method of magnetic microspheres under multiple magnetic control |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101341203A (en) * | 2005-12-09 | 2009-01-07 | 恰根有限公司 | Magnetic polymer particles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101341203A (en) * | 2005-12-09 | 2009-01-07 | 恰根有限公司 | Magnetic polymer particles |
Non-Patent Citations (3)
| Title |
|---|
| 孟繁宗等.荧光磁性微球Fe3O4@PMAA-Dy的制备和表征.《材料导报》.2008,第22卷(第6期),第134-136页. |
| 孟繁宗等.荧光磁性微球Fe3O4PMAA-Dy的制备和表征.《材料导报》.2008,第22卷(第6期),第134-136页. * |
| 杨旭等.表面含羧基的磁性高分子微球的制备和表征.《化学世界》.2006,(第5期),第276-280页. * |
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