CN106867021B - Preparation method of magnetic porous polymer microspheres - Google Patents
Preparation method of magnetic porous polymer microspheres Download PDFInfo
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- CN106867021B CN106867021B CN201510919870.3A CN201510919870A CN106867021B CN 106867021 B CN106867021 B CN 106867021B CN 201510919870 A CN201510919870 A CN 201510919870A CN 106867021 B CN106867021 B CN 106867021B
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Abstract
The invention discloses a preparation method of magnetic porous polymer microspheres. According to the invention, oleic acid is adopted to wrap magnetic ferric oxide nanoparticles, and then the magnetic nanoparticles are swelled into the pore channels of the porous polymer microsphere crosslinked by glycidyl methacrylate and ethylene glycol dimethacrylate, so as to obtain the magnetic porous polymer microsphere. The invention is characterized in that the porous polymer microsphere is taken as a template, the product parameters are controllable, the process operation is simple and easy, the raw material cost is low, the operation is simple and convenient, and the industrial implementation is easy.
Description
Technical Field
The invention relates to the technical field of magnetic microspheres, in particular to a preparation method of a magnetic porous polymer microsphere.
Background
The polymer magnetic nano-microsphere is a novel functional composite material. On the one hand due to the magnetic nanoparticlesThe polymer magnetic nano-microsphere can move along with the change of an external magnetic field, thereby realizing the rapid separation from the system; on the other hand, the organic surface of the polymer magnetic microsphere can be subjected to surface modification through abundant chemical reactions, and groups rich in various functionalities are introduced on the surface of the microsphere to enable the microsphere to have different surface functions and reactivity. The polymer magnetic nano-microsphere is a hotspot for studying magnetic functional materials by domestic and foreign scholars at present due to the good small-size effect, quantum size effect, surface effect and magnetic property, and the basic characteristics of softness, stability, easy processing and the like of a high polymer material, and is widely applied to the fields of biochemical separation, catalysis, medicine, environment and the like. The method for preparing the polymer magnetic nano-microsphere can be generally divided into a one-step method and a two-step method: the one-step method is that the magnetic nano material is added before balling, and the polymer is wrapped in the magnetic nano material during balling; the two-step method is that non-magnetic small balls are prepared, then magnetic materials enter the non-magnetic small balls through treatment, and finally magnetic nano particles exist in the skeleton materials of the microspheres in a dispersed form. Although the one-step method is developed earlier and applied more widely, the existing reports show that the reaction conditions are relatively harsh, the yield is too low, the content of functional groups in the magnetic composite microspheres is low, and the magnetic content is not high, so that the combination of the macromolecular magnetic composite microspheres and more biomacromolecules and inorganic particles is prevented, and the application of the expanded magnetic composite microspheres is greatly limited. Iron oxide (Fe)2O3) The magnetic source magnetic composite microsphere has the advantages of magnetic targeting property, small particle size of nanoparticles, large specific surface area, many surface atoms, high chemical activity and the like, and attracts high attention, such as documents (silk spinning, magnetic upsilon-Fe)2O3Preparation and performance research of the poly (styrene-divinylbenzene) composite material, and material report. 2008, 22, 136-138 and Fe complex2O3Structural characterization of polymer microspheres of nanoparticles, proceedings of higher school chemistry 1997,9,1565-1567) reported the preparation of polymer microspheres. These two methods have the following disadvantages: (1) the microspheres have poor dispersibility, not all in micron order; (2) pore diameter and distribution of the pore channel are poor, and non-pores and micropores exist; (3) the preparation method is complicated, and the parameters are not controllable; (4) magnetic propertyThe particles are not firmly adsorbed, and the particle size and the loading capacity are not controllable.
Disclosure of Invention
The invention provides a process method for synthesizing magnetic porous polymer microspheres by combining a template method with a seed polymerization method while swelling.
A preparation method of magnetic porous polymer microspheres adopts a template method combined with a swelling and polymerization method to prepare the magnetic porous microspheres.
As a preferable scheme of the invention, the method comprises the steps of wrapping magnetic ferric oxide nanoparticles by oleic acid, and swelling the magnetic nanoparticles into pore channels of the porous polymer microspheres crosslinked by glycidyl methacrylate and ethylene glycol dimethacrylate to obtain the magnetic porous polymer microspheres.
In a preferred embodiment of the present invention, the magnetic porous polymer microspheres have a particle size of 1 μm to 8 μm.
As a preferable scheme of the invention, the oil phase in the method comprises tetrahydrofuran and normal hexane; the water phase comprises methanol and deionized water solution.
As a preferred embodiment of the present invention, the above method comprises the steps of:
adding ferric chloride hexahydrate and sodium oleate into a mixed solvent of methanol, normal hexane and distilled water, uniformly mixing, heating to 85 ℃, reacting for 6 hours, taking an upper organic layer, washing with deionized water, and drying to obtain a paste precipitate;
adding 1-octadecene into the precipitate, protecting with nitrogen, heating to 400 ℃, preserving heat for 1h, cooling to room temperature, adding a mixed solution of n-hexane and methanol for precipitation, and performing centrifugal separation to obtain monodisperse magnetic nanoparticles wrapped by oleic acid;
dispersing the magnetic nano particles in tetrahydrofuran to prepare magnetic fluid, adding porous polymer microspheres, swelling for 1h, repeating for three times, and drying to obtain the magnetic porous polymer microspheres.
The invention has the advantages that: the monodispersity of the porous polymer microsphere template is good; the particle size of the porous polymer microsphere can be controlled by simply regulating and controlling experimental parameters; the pore size and the distribution of the porous polymer microspheres are controllable; the magnetic nano particles have controllable particle size, and the organic molecules coated on the surface of the magnetic nano particles are controllable in type; low cost of raw materials, simple and convenient process operation and easy industrial implementation.
Drawings
FIG. 1 is a schematic diagram of the reaction principle of the preparation method of the magnetic porous polymer microsphere of the present invention.
FIG. 2 is a schematic process diagram of the preparation method of the magnetic porous polymer microsphere of the present invention.
FIG. 3 is an SEM image of magnetic porous polymer microspheres prepared in example 1 of the present invention.
Detailed Description
The invention aims to overcome the defects of poor dispersity, uncontrollable pore size distribution and unsuitability for further functionalization of magnetic microspheres in the prior art, and provides a method for synthesizing the magnetic porous polymer microspheres by preparing monodisperse porous polymer microspheres and swelling magnetic nanoparticles into microsphere pore channels by using the monodisperse porous polymer microspheres as templates.
The invention firstly develops a novel method for synthesizing the magnetic porous polymer microsphere by using the glycidyl methacrylate and ethylene glycol dimethacrylate crosslinked porous polymer microsphere as a template and the oleic acid coated iron oxide nano particles as magnetic components and compounding the two components through swelling.
FIG. 1 shows a reaction principle schematic diagram of a preparation method of magnetic porous polymer microspheres, wherein the reaction is realized through adsorption.
Fig. 2 shows a process diagram of a preparation method of magnetic porous polymer microspheres, wherein smaller seeds form larger uniform seeds by swelling and polymerization.
The invention has the advantages that: the monodispersity of the porous polymer microsphere template is good; the particle size of the porous polymer microsphere can be controlled by simply regulating and controlling experimental parameters; the pore size and the distribution of the porous polymer microspheres are controllable; the magnetic nano particles have controllable particle size, and the organic molecules coated on the surface of the magnetic nano particles are controllable in type; low cost of raw materials, simple and convenient process operation and easy industrial implementation.
The process method for preparing the magnetic porous microspheres by using the porous polymer microspheres crosslinked by the glycidyl methacrylate and the ethylene glycol dimethacrylate as the template comprises the following steps:
the technological process of synthesizing silica microballoon with ammonia water as catalyst includes the following steps:
synthesizing magnetic iron oxide nano particles wrapped by oleic acid in a methanol, normal hexane and distilled water system, dispersing the nano particles in tetrahydrofuran to form magnetic fluid, adding a porous polymer microsphere template, and swelling the iron oxide nano particles into microsphere pore channels to obtain the magnetic porous polymer microspheres.
The process conditions are as follows: adding ferric chloride hexahydrate and sodium oleate into a mixed solvent of methanol, n-hexane and distilled water, uniformly mixing, and heating to 85 ℃ for reaction for 6 hours. The volume ratio of methanol to n-hexane to distilled water was 2:1: 2.5.
Adding 1-octadecene into the precipitate, protecting with nitrogen, heating to 400 ℃, preserving heat for 1h, cooling to room temperature, adding a mixed solution of n-hexane and methanol for precipitation, wherein the volume ratio of methanol to n-hexane is 5:1, and performing centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by oleic acid.
And dispersing the magnetic nanoparticles in tetrahydrofuran to prepare the magnetic fluid, wherein the concentration of the magnetic nanoparticle tetrahydrofuran dispersion liquid is 0.025-0.1 g/mL. Adding porous polymer microspheres, wherein the ratio of the magnetic nanoparticles to the polymer microspheres is 1: 0.5-3 by weight. Swelling for 1 h. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Example 1
10.8g of ferric chloride hexahydrate and 21.6g of sodium oleate are added into a mixed solvent of 100ml of methanol, 50ml of n-hexane and 125ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 23.9g of 1-octadecene into the precipitate, carrying out nitrogen protection, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature, adding 400ml of n-hexane methanol mixed solution for precipitation, and carrying out centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
And 4.5g of the magnetic nanoparticles are dispersed in 180ml of tetrahydrofuran to prepare magnetic fluid, and 2.25g of porous polymer microspheres are added to swell for 1 hour. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Fig. 3 shows an SEM image of the magnetic porous polymer microsphere prepared in example 1.
Example 2
5.4g of ferric chloride hexahydrate and 10.8g of sodium oleate are added into a mixed solvent of 100ml of methanol, 50ml of n-hexane and 125ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 11.5g of 1-octadecene into the precipitate, heating to 400 ℃ under the protection of nitrogen, preserving heat for 1h, cooling to room temperature, adding 400ml of n-hexane methanol mixed solution for precipitation, and performing centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
Dispersing 4.5g of the magnetic nanoparticles in 90ml of tetrahydrofuran to prepare magnetic fluid, adding 13.5g of porous polymer microspheres, and swelling for 1 h. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Example 3
6.5g of ferric chloride hexahydrate and 13.0g of sodium oleate are added into a mixed solvent of 120ml of methanol, 60ml of n-hexane and 150ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 13.8g of 1-octadecene into the precipitate, carrying out nitrogen protection, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature, adding 500ml of n-hexane methanol mixed solution for precipitation, and carrying out centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
5.4g of the magnetic nano particles are taken to be dispersed in 72ml of tetrahydrofuran to prepare magnetic fluid, 5.4g of porous polymer microspheres are added to swell for 1 hour. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Example 4
3.25g of ferric chloride hexahydrate and 6.5g of sodium oleate are added into a mixed solvent of 120ml of methanol, 60ml of n-hexane and 150ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 6.9g of 1-octadecene into the precipitate, carrying out nitrogen protection, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature, adding 500ml of n-hexane methanol mixed solution for precipitation, and carrying out centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
5.4g of the magnetic nano particles are taken to be dispersed in 54ml of tetrahydrofuran to prepare magnetic fluid, 4.05g of porous polymer microspheres are added to swell for 1 hour. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Example 5
8.64g of ferric chloride hexahydrate and 17.28g of sodium oleate are added into a mixed solvent of 160ml of methanol, 80ml of n-hexane and 140ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 18.4g of 1-octadecene into the precipitate, carrying out nitrogen protection, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature, adding 600ml of n-hexane methanol mixed solution for precipitation, and carrying out centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
And (3) dispersing 7.2g of the magnetic nanoparticles in 90ml of tetrahydrofuran to prepare magnetic fluid, adding 10.8g of porous polymer microspheres, and swelling for 1 h. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
Example 6
17.28g of ferric chloride hexahydrate and 34.56g of sodium oleate are added into a mixed solvent of 160ml of methanol, 80ml of n-hexane and 140ml of distilled water, and after uniform mixing, the mixture is heated to 85 ℃ for reaction for 6 hours. And taking the upper organic layer, washing with deionized water, and drying to obtain a paste precipitate.
Adding 4.6g of 1-octadecene into the precipitate, carrying out nitrogen protection, heating to 400 ℃, keeping the temperature for 1h, cooling to room temperature, adding 600ml of n-hexane methanol mixed solution for precipitation, and carrying out centrifugal separation to obtain the monodisperse magnetic nanoparticles wrapped by the oleic acid.
And (3) dispersing 7.2g of the magnetic nanoparticles in 72ml of tetrahydrofuran to prepare magnetic fluid, adding 14.4g of porous polymer microspheres, and swelling for 1 h. Repeating the steps for three times, and drying to obtain the magnetic porous polymer microspheres.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (3)
1. The preparation method of the magnetic porous polymer microsphere is characterized by comprising the steps of wrapping magnetic ferric oxide nanoparticles by oleic acid, and swelling the magnetic nanoparticles into a pore channel of the porous polymer microsphere crosslinked by glycidyl methacrylate and ethylene glycol dimethacrylate to obtain the magnetic porous polymer microsphere.
2. The preparation method according to claim 1, wherein the particle size of the magnetic porous polymer microsphere is 1 μm to 8 μm.
3. The method for preparing according to any one of claims 1-2, characterized in that the method comprises the steps of:
adding ferric chloride hexahydrate and sodium oleate into a mixed solvent of methanol, n-hexane and distilled water, uniformly mixing, and heating to 85 DEGoC, reacting for 6 hours, taking an upper organic layer, washing with deionized water, and drying to obtain a paste precipitate;
adding 1-octadecene into the precipitate, protecting with nitrogen, and heating to 400 deg.CoC, preserving heat for 1h, cooling to room temperature, adding a mixed solution of normal hexane and methanol for precipitation, and performing centrifugal separation to obtain monodisperse magnetic nanoparticles wrapped by oleic acid;
dispersing the magnetic nano particles in tetrahydrofuran to prepare magnetic fluid, adding porous polymer microspheres, swelling for 1h, repeating for three times, and drying to obtain the magnetic porous polymer microspheres.
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| CN102049225A (en) * | 2009-10-30 | 2011-05-11 | 北京大学深圳研究生院 | Method for preparing superparamagnetic polymer microspheres |
| CN103012242A (en) * | 2012-12-31 | 2013-04-03 | 北京大学深圳研究生院 | Preparation method of 3-substituted indole derivatives |
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| CN102049225A (en) * | 2009-10-30 | 2011-05-11 | 北京大学深圳研究生院 | Method for preparing superparamagnetic polymer microspheres |
| CN103012242A (en) * | 2012-12-31 | 2013-04-03 | 北京大学深圳研究生院 | Preparation method of 3-substituted indole derivatives |
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| Title |
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| "Improved functionalization of oleic acid-coated iron oxide nanoparticles for biomedical applications";Maarten Bloemen et al.;《Journal of nanoparticle research》;20121231;第14卷;第1-10页 * |
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