CN102408520B - Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere - Google Patents
Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere Download PDFInfo
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Abstract
The invention relates to a preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere used for solving the technical problems of low magnetism response of the monodisperse ferrate nano magnetic beads prepared through the current preparation method. A technical scheme is as follows: nano monodisperse high magnetism response Fe3O4 prepared through a solvothermal method is used as a nucleus and acrylic acid monomers are used as functional monomers to prepare nano cross-linking degree nuclear shell magnetic polymer microsphere comprising carboxyl on surface with monodisperse high magnetism response and high magnetism content. Compared with the traditional preparation method for magnetic balls, both the monodisperse performance and magnetism response of the magnetic balls prepared through the method are greatly improved, and the magnetism response is improved by 68.4-80.1emu/g. The monodisperse polymer microspheres with preset grain sizes can be obtained in advance through conventional precipitation polymerization reaction as long as proper dosage of cross-linking agent and acrylic acid monomers is selected.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic polymer microsphere, particularly relate to the preparation method that a kind of nano level list disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
Background technology
Magnetic macromolecular microsphere due to have simultaneously the magnetic responsiveness of inorganic magnetic material and organic macromolecule surface-functional (as-COOH ,-OH ,-NH
2,-SH etc.), can be easily and fast under externally-applied magnetic field, separated from medium efficiently, so it is with a wide range of applications in fields such as medical science, molecular biology, biological chemistries.
At present, the preparation method of magnetic composite microsphere mainly contains emulsifier-free emulsion polymerization, mini-emulsion polymerization, dispersion polymerization, suspension polymerization, conversed phase micro emulsion copolymerization etc.But letex polymerization obtains monodispersed submicron order spherical particle conventionally, although suspension polymerization can obtain micron level spherical particle, yet size distribution is wider.In addition, magnetic content and the magnetic responsiveness of the magnetic microsphere that above method obtains are all lower, and need with suitable tensio-active agent.
Document " publication number is the Chinese invention patent of CN1645530 " discloses a kind of method of synthesizing series monodisperse ferrate nanometer magnetic bead.It is raw material that the method be take solubility ferric ion salt, in ethylene glycol solution, carries out solvent thermal reaction at 200～300 ℃, forms Fe
3o
4nanometer magnetic bead.Under identical reaction conditions, by adding the salt of one or more divalence soluble metal ions, jointly react with solubility ferric ion salt, control addition, the mol ratio that makes divalent-metal ion and ferric ion is 0.01～1: 2, forms ferrite nano magnetic bead and complex ferrite nanometer magnetic bead.But the shortcoming that monodisperse ferrate nanometer magnetic bead prepared by the method exists is that magnetic responsiveness is low.
Summary of the invention
In order to overcome the prepared low deficiency of monodisperse ferrate nanometer magnetic bead magnetic responsiveness of existing preparation method, the invention provides the preparation method that a kind of nano level list disperses high magnetic responsiveness core-shell magnetic polymer microballoon.Single high magnetic responsiveness Fe of dispersion that the method is prepared with solvent-thermal method
3o
4for core, using acrylic monomer as functional monomer, by precipitation polymerization method, prepare high magnetic responsiveness and high magnetic content and surperficial carboxylic nano level list and disperseed high-crosslinking-degree core-shell magnetic polymer microballoon.
The technical solution adopted for the present invention to solve the technical problems is: a kind of nano level list disperses the preparation method of high magnetic responsiveness core-shell magnetic polymer microballoon, is characterized in comprising the following steps:
(1), in being furnished with the reactor of prolong, add the acetonitrile of 85～100wt% and the alcohol of 0～15wt%;
(2) by the Fe of relative monomer mixed solution 3～17wt%
3o
4microballoon joins in the above-mentioned reactor that acetonitrile and alcohol are housed;
(3) take the linking agent monomer of 50～100wt% and the monomer mixed solution that 0～50wt% acrylic monomer forms, and the initiator of monomer mixed solution 0.1～5wt%, vibration joins in above-mentioned reactor after dissolving, and mixes;
(4) above-mentioned reactor is progressively warming up to 65～85 ℃, polymerization 8～20h;
(5) product step (4) being obtained carries out magnetic separation, and the upper strata liquid that inclines adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, obtains surperficial carboxylic nano level list and disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
The invention has the beneficial effects as follows: due to the single high magnetic responsiveness Fe of dispersion preparing with solvent-thermal method
3o
4for core, acrylic monomer, as function monomer, has been prepared the carboxylic single nano level high-crosslinking-degree core-shell magnetic polymer microballoon that disperses high magnetic responsiveness and high magnetic content in a kind of surface by precipitation polymerization method.Compare with traditional magnetic ball preparation method, the standby magnetic ball of this legal system is all being greatly improved aspect monodispersity and magnetic responsiveness, and magnetic responsiveness is brought up to 68.4～80.1emu/g.Only need to select suitable linking agent and the consumption of acrylic monomer, through conventional precipitation polymerization reaction, both can obtain the monodisperse magnetic polymer microballoon of predefined particle diameter.Meanwhile, owing to thering is reactive carboxylic group in function monomer, can meet the numerous areas such as biotechnology and separation engineering and the nano level list of different-grain diameter be disperseed to the demand of nucleocapsid magnetic microsphere.
Below in conjunction with drawings and Examples, the present invention is elaborated.
Accompanying drawing explanation
Fig. 1 is the TEM photo that the nano level list of embodiment 3 preparations disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
Fig. 2 is the TEM photo that the nano level list of embodiment 6 preparations disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
Embodiment
Embodiment 1: in being furnished with the 100mL reactor of prolong, add 68g acetonitrile and 12g methyl alcohol; By 0.012g Fe
3o
4microballoon joins in 100mL reactor; By 0.13g EGDMA (ethylene glycol dimethacrylate) and the monomer mixed solution of 0.02g MAA (methacrylic acid) composition and the AIBN (Diisopropyl azodicarboxylate) of 0.001g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 65 ℃, polymerization 14h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 480nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 80.1emu/g, and magnetic content is 94.8wt%.
Embodiment 2: in being furnished with the 100mL reactor of prolong, add 65g acetonitrile and 8g propyl carbinol; By 0.028g Fe
3o
4microballoon joins in 100mL reactor; By 0.25g EGDMA (ethylene glycol dimethacrylate) and the monomer mixed solution of 0.14g AA (vinylformic acid) composition and the BPO (dibenzoyl peroxide) of 0.003g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 80 ℃, polymerization 10h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 495nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 76.8emu/g, and magnetic content is 93.5wt%.
Embodiment 3: in being furnished with the 100mL reactor of prolong, add 75g acetonitrile and 5g Virahol; By 0.034g Fe
3o
4microballoon joins in 100mL reactor; By 0.39g DVB (Vinylstyrene) and the monomer mixed solution of 0.22gMAA (methacrylic acid) composition and the AIBN (Diisopropyl azodicarboxylate) of 0.009g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 84 ℃, polymerization 8h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 539nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 75.5emu/g, and magnetic content is 92.1wt%.
Embodiment 4: in being furnished with the 150mL reactor of prolong, add 79g acetonitrile and 12g ethanol; By 0.071g Fe
3o
4microballoon joins in 150mL reactor; By 0.58g EGDMA (ethylene glycol dimethacrylate) and the monomer mixed solution of 0.41g MAA (methacrylic acid) composition and the BPO (dibenzoyl peroxide) of 0.014g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 79 ℃, polymerization 20h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 574nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 73.8emu/g, and magnetic content is 91.1wt%.
Embodiment 5: in being furnished with the 150mL reactor of prolong, add 90g acetonitrile and 10g n-propyl alcohol (or isopropylcarbinol); By 0.085g Fe
3o
4microballoon joins in 150mL reactor; By 0.68g DVB (Vinylstyrene) and the monomer mixed solution of 0.51g AA (vinylformic acid) composition and the BPO (dibenzoyl peroxide) of 0.018g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 85 ℃, polymerization 15h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 591nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 72.9emu/g, and magnetic content is 89.4wt%.
Embodiment 6: in being furnished with the 150mL reactor of prolong, add 110g acetonitrile; By 0.15g Fe
3o
4microballoon joins in 150mL reactor; By 1.0g DVB (Vinylstyrene) and the monomer mixed solution of 1.0g MAA (methacrylic acid) composition and the AIBN (Diisopropyl azodicarboxylate) of 0.021g, vibration joins in reactor after dissolving, and mixes; Progressively be warming up to 65 ℃, polymerization 18h; The product obtaining is carried out to magnetic separation, and the upper strata liquid that inclines, adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance.At room temperature vacuum-drying, the nano level list that obtains dark brown disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
After tested, it is 630nm that resulting nano level list disperses high magnetic responsiveness core-shell magnetic polyalcohol microspherulite diameter, and magnetic responsiveness is 68.4emu/g, and magnetic content is 86.1wt%.
Claims (4)
1. nano level list disperses a preparation method for high magnetic responsiveness core-shell magnetic polymer microballoon, it is characterized in that comprising the steps:
(1), in being furnished with the reactor of prolong, add the acetonitrile of 85～100wt% and the alcohol of 0～15wt%;
(2) by the Fe of relative monomer mixed solution 3～17wt%
3o
4microballoon joins in the above-mentioned reactor that acetonitrile and alcohol are housed;
(3) take the monomer mixed solution that linking agent monomer and Acrylic Acid Monomer or methacrylic acid monomer form, and the initiator of monomer mixed solution 0.1～5wt%, 50wt%≤linking agent monomer content < 100wt%, 0 < Acrylic Acid Monomer or methacrylic acid monomer content≤50wt%, after vibration is dissolved, join in above-mentioned reactor, mix;
(4) above-mentioned reactor is progressively warming up to 65～85 ℃, polymerization 8～20h;
(5) product step (4) being obtained carries out magnetic separation, and the upper strata liquid that inclines adds dehydrated alcohol through ultrasonic dispersion, and then carries out magnetic separation; So repetitive scrubbing several times, to remove unnecessary monomer and polymkeric substance; At room temperature vacuum-drying, obtains surperficial carboxylic nano level list and disperses high magnetic responsiveness core-shell magnetic polymer microballoon.
2. preparation method according to claim 1, is characterized in that: described linking agent be Vinylstyrene or ethylene glycol dimethacrylate any.
3. preparation method according to claim 1, is characterized in that: described initiator be Diisopropyl azodicarboxylate or dibenzoyl peroxide any.
4. preparation method according to claim 1, is characterized in that: described alcohol is any of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
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| CN104250327A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing particle size-controllable high-crosslinked monodispersed polydivinylbenzene microspheres |
| CN106117402B (en) * | 2016-07-04 | 2017-11-28 | 中北大学 | High-performance magnetorheological nano composite polymeric gel process for preparing |
| CN109939621B (en) * | 2019-03-08 | 2020-08-11 | 清华大学 | Method for preparing single-particle uniform coating shell layer by liquid phase interface crossing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645530A (en) * | 2004-11-12 | 2005-07-27 | 清华大学 | Method for synthesizing series single-dispersed ferrite nanometer magnetic beads |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
| CN101608020A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院理化技术研究所 | With the standby magnetic Fe that obtains of hydro-thermal legal system 3O 4Polymer sub-micron sphere and purposes |
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2011
- 2011-09-22 CN CN201110284936.8A patent/CN102408520B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645530A (en) * | 2004-11-12 | 2005-07-27 | 清华大学 | Method for synthesizing series single-dispersed ferrite nanometer magnetic beads |
| CN101608020A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院理化技术研究所 | With the standby magnetic Fe that obtains of hydro-thermal legal system 3O 4Polymer sub-micron sphere and purposes |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
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