CN111359551A - Magnetic polymer microsphere and preparation method thereof - Google Patents
Magnetic polymer microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN111359551A CN111359551A CN202010210863.7A CN202010210863A CN111359551A CN 111359551 A CN111359551 A CN 111359551A CN 202010210863 A CN202010210863 A CN 202010210863A CN 111359551 A CN111359551 A CN 111359551A
- Authority
- CN
- China
- Prior art keywords
- microspheres
- magnetic
- chain fatty
- fatty acid
- long
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Hard Magnetic Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a magnetic polymer microsphere and a preparation method thereof. Firstly, modifying the surface of the magnetic nanoparticles by using medium-short chain fatty acid during magnetic particle synthesis to increase the polarity of the surface of the magnetic nanoparticles, so that the magnetic nanoparticles are uniformly dispersed in a good solvent and have more uniform particle size; and then, a swelling method is adopted to enable the magnetic nano particles to enter the swelled polymer microspheres, the swelling degree of the monodisperse polymer microspheres is regulated and controlled through the proportion of a good swelling agent and a poor solvent in the system, the number of the magnetic nano particles entering the microspheres is further regulated and controlled, the saturation magnetization is regulated, then the microspheres are deswelled in the poor solvent, and cracked holes generated on the surfaces of the microspheres due to the swelling effect are sealed, so that the leakage of the magnetic nano particles is avoided. The preparation method has mild conditions, simple operation and easily obtained raw materials, greatly reduces the cost of the method, enlarges the universality of the method, is easy for industrial production, and has small CV of the particle size of the obtained magnetic polymer microsphere.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a magnetic polymer microsphere and a preparation method thereof.
Background
The magnetic microsphere is a novel magnetic material developed in recent years, and has unique advantages in the biomedical field due to the magnetism, the high specific surface area and the possibility of modifying various functional groups on the surface. Especially has very wide application prospect in the directions of in vitro diagnosis, cell separation, immunodetection, protein separation and purification and the like. In vitro diagnostic applications, the requirements for magnetic microspheres are particularly stringent. The magnetic microspheres used in the field should have a relatively high magnetic separation speed, i.e., a relatively high saturation magnetization; the particle size distribution is uniform, and the particle size CV is smaller; at the same time, the surface has a large number of functional groups for coupling antibodies.
The existing methods for preparing the magnetic microspheres mainly comprise an embedding method, a polymerization method and an in-situ growth method. However, the existing preparation method or process is complex and is not beneficial to large-scale production; or the microsphere has poor dispersibility and wide size distribution; or the number and the types of the surface functional groups are insufficient, so that the application value of the composite material is limited; or using dangerous control chemical reagents such as easy poison control and the like.
Chinese patent CN200910110365.9 discloses a method for obtaining superparamagnetic polymer microspheres by permeating long-chain fatty acid iron, such as iron oleate molecules into polymer microspheres by using a swelling technique, and then decomposing the long-chain fatty acid iron, such as iron oleate molecules into the microspheres by raising the temperature to synthesize magnetic ferroferric oxide nanoparticles. Although the method has simple preparation process and lower cost, the polystyrene microspheres need to be subjected to a high temperature process (200-350 ℃) in the preparation process, and the polystyrene microspheres are easy to adhere at the high temperature to form polymers, so that the method is not beneficial to the application of the polystyrene microspheres in the field of in vitro diagnosis.
Chinese patent CN201010129442.8 discloses a method for preparing magnetic fluorescent microspheres with polystyrene microspheres as carriers. The method requires the use of chloroform as described. Chloroform, as an easily toxic chemical and a highly toxic substance, is extremely strictly controlled, and therefore, is very unfavorable for production conversion and subsequent scale-up production. The particle size distribution range of the used microspheres is only within the range of 5-10 micrometers, and the universality of the method is restricted. In addition, the preparation period of the method is long (about 12-48 hours), and the production efficiency is influenced. And the magnetic separation time of the microsphere prepared by the patent is 30 minutes, which greatly limits the application prospect of the microsphere in the field of in vitro diagnosis.
US4774265 uses monodisperse macroporous polystyrene microspheres, which are first nitrated or sulfonated and then grown with magnetic particles in the pores. But because the leakage of the magnetic particles is worried, a layer of polymer is coated on the surface to seal the pore channel. The method has complex process, low yield and is not suitable for large-scale production.
In chinese patent CN 101044213B, aqueous phase magnetic particles larger than 10nm are used and fixed on the surface of polystyrene microsphere, and then polymer wrapping is performed to complete the fixation. The magnetic microsphere prepared by the method has good magnetic response and ideal CV. But also has complex preparation process and high cost.
Disclosure of Invention
Therefore, a preparation method which is mild in condition, simple in process, beneficial to industrial production and capable of obtaining the magnetic polymer microspheres with high saturation magnetization and small particle size CV is needed.
The technical scheme is as follows:
a preparation method of magnetic polymer microspheres comprises the following steps:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, and heating to obtain the magnetic nanoparticles;
dissolving monodisperse polymer microspheres in poor solvent α 1 to obtain mixture A, and dissolving magnetic nanoparticles in good solvent β to obtain mixture B;
mixing the mixture A and the mixture B, and deswelling the mixture B by using a poor organic solvent 2 after reaction to obtain the magnetic polymer microspheres;
wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-200: 1.
In one embodiment, the volume ratio of the poor solvent α 1 to the good solvent β is 1:1 to 100: 1.
In one embodiment, the mixing time of the mixture A and the mixture B is 0.5h to 6 h.
In one embodiment, the poor solvent α 1 and the poor solvent α 2 are each independently selected from at least one of ethanol, methanol, isopropanol, ethanol, ethylene glycol, propanol, n-octanol, undecanol, isobutanol, and n-propanol.
In one embodiment, the good solvent β is selected from at least one of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, 1, 2-dichloroethane, and trichloroethane.
In one embodiment, the mass ratio of the monodisperse polymeric microspheres to the magnetic nanoparticles is 10: 1-10000: 1.
in one embodiment, the magnetic nanoparticles have a particle size of 1nm to 100 nm.
In one embodiment, the monodisperse microspheres are selected from at least one of polystyrene microspheres, polymethyl methacrylate microspheres, agarose microspheres, polystyrene-divinylbenzene microspheres, and methyl methacrylate-glycerol methacrylate microspheres.
In one embodiment, the monodisperse polymer microsphere has a particle size of 0.1 μm to 1000. mu.m.
In one embodiment, the step of mixing the long-chain fatty acid, the medium-short chain fatty acid and the iron long-chain fatty acid, and heating to obtain the magnetic nanoparticles comprises:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, heating to 200-400 ℃, and reacting for 1-12 h;
the hydrocarbon chain length X of the long-chain fatty acid1Satisfies the following conditions: x is not less than 131≤40；
The hydrocarbon chain length X of the medium-short chain fatty acid2Satisfies the following conditions: x is not less than 32≤12；
The volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1: 1-100: 1.
The invention also provides the magnetic polymer microsphere obtained by the preparation method in any embodiment.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly introduces a proper amount of medium-short chain fatty acid to modify the surface of the magnetic nanoparticles, which does not affect the saturation magnetization of the product, but also can increase the polarity of the surface of the magnetic nanoparticles, so that the magnetic nanoparticles can be uniformly dispersed in good solvent β, the particle size is more uniform, then a swelling method is adopted to enable the magnetic nanoparticles to enter the swollen polymer microspheres, the swelling degree of the monodisperse polymer microspheres can be controlled by regulating the ratio of good swelling agent to poor solvent α in the swelling system, the number of the magnetic nanoparticles entering the microspheres is regulated, the saturation magnetization is regulated, then the microspheres can swell and subside in the poor solvent α, the cracked pores on the surface of the polymer microspheres due to the swelling effect are sealed, the leakage of the magnetic nanoparticles is avoided, and the sealing process is simplified.
Drawings
FIG. 1 is a transmission electron micrograph of the magnetic nanoparticles obtained in example 3;
FIG. 2 is a scanning electron micrograph of the magnetic polymer microspheres obtained in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the long-chain fatty acid refers to a fatty acid having a hydrocarbon chain length of more than 12C. Medium-short chain fatty acids refer to fatty acids with a hydrocarbon chain length between 3C and 12C. The long-chain fatty acid iron refers to fatty acid iron with a hydrocarbon chain length of more than 12C.
The technical scheme is as follows:
a preparation method of magnetic polymer microspheres comprises the following steps:
a preparation method of magnetic polymer microspheres comprises the following steps:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, and heating to obtain the magnetic nanoparticles;
dissolving monodisperse polymer microspheres in poor solvent α 1 to obtain mixture A, and dissolving magnetic nanoparticles in good solvent β to obtain mixture B;
mixing the mixture A and the mixture B, and deswelling the mixture B by using a poor organic solvent 2 after reaction to obtain the magnetic polymer microspheres;
wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-200: 1.
The monodisperse polymer microsphere has the characteristic of being capable of infinitely swelling until being dissolved in the good swelling agent, and the swelling degree of the polymer microsphere can be controlled by regulating the proportion of the good swelling agent to the poor solvent α in the swelling system, the number of the magnetic nanoparticles entering the polymer microsphere can be regulated, and the saturation magnetization can be regulated.
The invention firstly introduces a proper amount of medium-short chain fatty acid to modify the surface of the magnetic nanoparticles, which does not affect the saturation magnetization of the product, but also can increase the polarity of the surface of the magnetic nanoparticles, so that the magnetic nanoparticles can be uniformly dispersed in good solvent β, the particle size is more uniform, then a swelling method is adopted to enable the magnetic nanoparticles to enter the swollen polymer microspheres, the swelling degree of the monodisperse polymer microspheres can be controlled by regulating the ratio of good swelling agent to poor solvent α in the swelling system, the number of the magnetic nanoparticles entering the polymer microspheres is regulated, the saturation magnetization is regulated, then the effect of swelling and fading of the polymer microspheres in poor solvent α is utilized to seal the pores on the surface of the polymer microspheres due to the swelling effect, so that the leakage of the magnetic nanoparticles is avoided, and the sealing process is simplified.
The preparation method of the magnetic polymer microsphere mainly comprises the following steps: (1) preparing magnetic nanoparticles; (2) and preparing the magnetic polymer microspheres.
Preferably, in the present invention, the step (1) comprises:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, heating to 200-400 ℃, and reacting for 1-4 h;
the hydrocarbon chain length X of the long-chain fatty acid1Satisfies the following conditions: x is not less than 131≤40；
The hydrocarbon chain length X of the medium-short chain fatty acid2Satisfies the following conditions: x is not less than 32≤12；
The volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1: 1-100: 1.
Wherein, the hydrocarbon chain length refers to the number of carbon atoms.
In the present invention, the volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1:1 to 100:1, and it is understood that the volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid may be set to, but not limited to: 1:1, 1.12:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 10:1, 11.2:1, 13.5:1, 14:1, 16:1, 20:1, 30:1, 40:1, 50:1, 60.3:1, 70:1, 75:1, 80:1, 85.6:1, 90:1, and 100: 1. Preferably, the volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1: 1-70: 1.
According to the invention, a proper amount of medium-short chain fatty acid is introduced to modify the surface of the magnetic nanoparticles, so that the saturation magnetization intensity of the product is not influenced, the polarity of the surface of the magnetic nanoparticles can be increased, the magnetic nanoparticles can be uniformly dispersed in the good solvent β, and the particle size is more uniform.
Preferably, the step (1) in the present invention comprises:
mixing the long-chain fatty acid, the medium-short chain fatty acid and the long-chain fatty acid iron, heating to 260-330 ℃, and reacting for 1.5-2 h;
the hydrocarbon chain length X of the long-chain fatty acid1Satisfies the following conditions: x is more than or equal to 181≤36；
The hydrocarbon chain length X of the medium-short chain fatty acid2Satisfies the following conditions: x is not less than 82Less than or equal to 10; the volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1: 1-50: 1.
More preferably, the long chain fatty acid is oleic acid. More preferably, the medium-short chain fatty acid is lauric acid. Further preferably, the iron long-chain fatty acid is iron oleate.
Preferably, the iron long-chain fatty acid is prepared by a preparation method comprising the following preparation steps:
mixing Fe3+Mixing salt, long-chain fatty acid sodium, cyclohexane, ethanol and water, controlling the reaction temperature to be 50-90 ℃, and reacting for 1-96 hours to obtain the long-chain fatty acid iron.
In some preferred embodiments, the Fe3+The salt is selected from ferric chloride, ferric sulfate or ferric nitrate.
Preferably, in the present invention, the step (2) includes:
dissolving the monodisperse polymer microspheres in poor solvent α 1 to obtain a mixture A;
dissolving the magnetic nanoparticles obtained in the step (1) in a good solvent β to obtain a mixture B;
and adding the mixture B into the mixture A, reacting for 0.5-6 h, and deswelling by using a poor organic solvent 2 to obtain the magnetic polymer microsphere.
Wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-200: 1.
In the present invention, the volume ratio of the poor solvent α 1 to the good solvent β is 1:1 to 200:1, and it is understood that the volume ratio of the poor solvent α 1 to the good solvent β may be, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 10:1, 12.5:1, 16:1, 20.1:1, 23:1, 25:1, 26.4:1, 35:1, 40:1, 45.8:1, 50:1, 55:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, and 200:1, and preferably, the volume ratio of the poor solvent α 1 to the good solvent β is 1 to 100: 1.
In some preferred embodiments, the reaction time of the mixture a and the mixture B is 0.5h to 3 h; more preferably, the reaction time is 0.5h to 2 h.
In some preferred embodiments, the step (2) comprises:
dissolving the monodisperse polymer microspheres in poor solvent α 1, and stirring to obtain a mixture A;
dissolving the magnetic nanoparticles obtained in the step (1) in a good solvent β, and stirring to obtain a mixture B;
adding the mixture B into the mixture A, stirring and reacting for 0.5-3 h, and then deswelling with a poor organic solvent 2 to obtain the magnetic polymer microspheres;
wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-100: 1.
In some preferred embodiments, the poor solvent α 1 and the poor solvent α 2 are each independently selected from at least one of ethanol, methanol, isopropanol, ethanol, ethylene glycol, propanol, n-octanol, undecanol, isobutanol, and n-propanol.
In some preferred embodiments, the good solvent β is selected from at least one of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, 1, 2-dichloroethane, and trichloroethane.
In some of the more preferred embodiments, the good solvent β is selected from dichloromethane.
The method comprises the steps of using dichloromethane as a good solvent β to avoid using chloroform reagents which are easy to prepare toxicity and extremely toxic, controlling the swelling degree of monodisperse polymer microspheres by adjusting the ratio of the good swelling agent to a poor solvent α in a swelling system, regulating the number of magnetic nanoparticles entering the microspheres, adjusting the saturation magnetization, and sealing the surface of the microspheres with the aid of the swelling and fading effect of the microspheres in the poor solvent α to prevent the magnetic nanoparticles from leaking and simplify the sealing process.
The preparation method has mild reaction conditions, does not need high temperature, does not cause adhesion of the polymer microspheres, and is beneficial to the application of the polymer microspheres in the field of in vitro diagnosis; moreover, the preparation method is simple to operate, raw materials are easy to obtain, the cost of the method is greatly reduced, the universality of the method is enlarged, and the industrial production is easy to realize.
In some preferred embodiments, the mass ratio of the monodisperse polymeric microspheres to the magnetic nanoparticles is 10: 1-10000: 1. it is understood that, in the present invention, the mass ratio of the monodisperse polymer microspheres to the magnetic nanoparticles can be set as, but is not limited to: 10:1, 12:1, 13:1, 14:1, 25:1, 30:1, 32.5:1, 33.2:1, 40.1:1, 53:1, 65:1, 76.4:1, 85:1, 90:1, 95.8:1, 100:1, 105:1, 120:1, 130:1, 1400:1, 150:1, 160.2:1, 170:1, 180.3:1, 190:1, 190.6:1, 200:1, 250:1, 268:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, and 10000: 1.
In some preferred embodiments, the magnetic nanoparticles have a particle size of 1nm to 100 nm. Preferably, the magnetic nanoparticles have a particle size of 1nm, 4nm, 10nm, 16nm and 100 nm.
In some preferred embodiments, the monodisperse microspheres are selected from at least one of polystyrene microspheres, polymethyl methacrylate microspheres, agarose microspheres, polystyrene-divinylbenzene microspheres, and methyl methacrylate-glycerol methacrylate microspheres. Preferably, the monodisperse polymer microspheres are selected from monodisperse carboxy polystyrene microspheres, amino polystyrene microspheres, epoxy polystyrene microspheres or mercapto polystyrene microspheres.
In some preferred embodiments, the monodisperse polymeric microspheres have a particle size of 0.1 μm to 1000 μm. Preferably, the particle size of the monodisperse polymer microspheres is 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 5 μm, 6 μm, 10 μm, 20 μm and 100 μm.
The invention also provides the magnetic polymer microsphere obtained by the preparation method.
In the following, specific examples are shown, and the starting materials used in the examples of the present invention are all commercially available, unless otherwise specified.
Example 1
This example provides a magnetic polymer microsphere and a method for preparing the same
a. Preparing iron oleate:
5.4g FeCl was added to the system318.3g sodium oleate, 120mL absolute ethyl alcohol, 120mL cyclohexane and 120mL deionized water, reflux at 70 ℃ for 96 h. After absorbing the bottom deionized water, repeatedly cleaning for 3 times by using the deionized water to obtain an iron oleate solution;
b. preparing magnetic nanoparticles with the particle size of 4 nm:
120mL of octadecene was added to the iron oleate solution, magnetically stirred at 100 ℃ to remove cyclohexane, then 8mL of oleic acid and 10mL of n-octanoic acid were added, and the temperature was raised to 290 ℃ for reaction for 8 h. After the reaction is stopped, cleaning with ethanol, removing octadecene and unreacted substances to obtain black precipitate, and obtaining magnetic nanoparticles with the particle size of 4 nm;
weighing 100mg of magnetic nanoparticles with the particle size of 4nm, dissolving the magnetic nanoparticles in 10mL of dichloromethane, and dispersing the magnetic particles uniformly by using ultrasound to obtain a mixture A;
c. preparing magnetic polymer microspheres with the particle size of 1 mu m:
weighing 1g of non-crosslinked carboxyl polystyrene microspheres with the particle size of 1 mu m, and dissolving in 100mL of ethanol to obtain a mixture B; and adding the mixture A into the mixture B, shaking for 1h, stopping the reaction, and alternately cleaning the product with ethanol and water for three times to obtain the magnetic polymer microspheres with the particle size of 1 mu m.
The morphology and magnetization properties of the magnetic polymer microspheres obtained in this example were characterized.
Example 2
This example provides a magnetic polymer microsphere and a method for preparing the same
a. Preparing iron oleate:
5.4g FeCl was added to the system318.3g of sodium oleate, 120mL of anhydrous sodium oleateEthanol, 120mL cyclohexane and 120mL deionized water, at 70 ℃ under reflux for 96 h. After absorbing the bottom deionized water, repeatedly cleaning for 3 times by using the deionized water to obtain an iron oleate solution;
b. preparing magnetic nanoparticles with the particle size of 10 nm:
adding 120mL of octadecene into the iron oleate solution, magnetically stirring at 100 ℃, removing cyclohexane, then adding 10mL of oleic acid and 50mL of n-octanoic acid, and heating to 320 ℃ for reaction for 6 h. After the reaction is stopped, cleaning with ethanol, removing octadecene and unreacted substances to obtain black precipitate, and obtaining magnetic nanoparticles with the particle size of 10 nm;
weighing 100mg of magnetic nanoparticles with the particle size of 10nm, dissolving the magnetic nanoparticles in 10mL of dichloromethane, and dispersing the magnetic particles uniformly by using ultrasound to obtain a mixture A;
c. preparing magnetic polymer microspheres with the particle size of 10 mu m:
weighing 1g of non-crosslinked carboxyl polystyrene microspheres with the particle size of 10 mu m, and dissolving in 100mL of ethanol to obtain a mixture B; and adding the mixture A into the mixture B, shaking for 1h, stopping the reaction, and alternately cleaning the product with ethanol and water for three times to obtain the magnetic polymer microspheres with the particle size of 10 microns.
The morphology and magnetization properties of the magnetic polymer microspheres obtained in this example were characterized.
Example 3
This example provides a magnetic polymer microsphere and a method for preparing the same
a. Preparing iron oleate:
5.4g FeCl was added to the system318.3g sodium oleate, 120mL absolute ethyl alcohol, 120mL cyclohexane and 120mL deionized water, reflux at 70 ℃ for 96 h. After absorbing the bottom deionized water, repeatedly cleaning for 3 times by using the deionized water to obtain an iron oleate solution;
b. preparing magnetic nanoparticles with the particle size of 16 nm:
120mL of octadecene was added to the iron oleate solution, magnetically stirred at 100 ℃ to remove cyclohexane, and then 15mL of oleic acid and 20mL of n-octanoic acid were added, and the temperature was raised to 330 ℃ for reaction for 5 hours. After the reaction is stopped, cleaning with ethanol, removing octadecene and unreacted substances to obtain black precipitate, and obtaining magnetic nanoparticles with the particle size of 16 nm;
weighing 100mg of magnetic nanoparticles with the particle size of 16nm, dissolving the magnetic nanoparticles in 10mL of dichloromethane, and uniformly dispersing the magnetic particles by using ultrasound to obtain a mixture A;
c. preparing magnetic polymer microspheres with the particle size of 100 mu m:
weighing 1g of non-crosslinked carboxyl polystyrene microspheres with the particle size of 100 mu m, and dissolving in 100mL of ethanol to obtain a mixture B; and adding the mixture A into the mixture B, shaking for 1h, stopping the reaction, and alternately cleaning the product with ethanol and water for three times to obtain the magnetic polymer microspheres with the particle size of 100 microns.
The morphology of the magnetic polymer microspheres obtained in this example was characterized.
Fig. 1 is a transmission electron microscope image of the magnetic polymer microsphere obtained in this embodiment, and it can be seen from the image that the magnetic polymer microsphere obtained in this embodiment has good particle uniformity and small particle size CV.
Example 4
This example provides a magnetic polymer microsphere and a method for preparing the same
a. Preparing iron oleate:
4g of Fe was added to the system2(SO4)312g of sodium oleate, 100mL of absolute ethanol, 80mL of cyclohexane and 120mL of deionized water, and refluxing at 85 ℃ for 1 h. After absorbing the bottom deionized water, repeatedly cleaning for 3 times by using the deionized water to obtain an iron oleate solution;
b. preparing magnetic nanoparticles with the particle size of 10 nm:
200mL of octadecene was added to the iron oleate solution, magnetically stirred at 100 ℃ to remove cyclohexane, then 10mL of oleic acid and 1mL of stearic acid were added, and the temperature was raised to 300 ℃ for reaction for 2 h. After the reaction is stopped, cleaning with ethanol, removing octadecene and unreacted substances to obtain black precipitate, and obtaining magnetic nanoparticles with the particle size of 10 nm;
weighing 100mg of magnetic nanoparticles with the particle size of 10nm, dissolving the magnetic nanoparticles in 10mL of dichloromethane, and dispersing the magnetic particles uniformly by using ultrasound to obtain a mixture A;
c. preparing magnetic polymer microspheres with the particle size of 5 mu m:
weighing 1g of non-crosslinked carboxyl polystyrene microspheres with the particle size of 5 mu m, and dissolving in 300mL of ethanol to obtain a mixture B; and adding the mixture A into the mixture B, shaking for 1h, stopping the reaction, and alternately cleaning the product with ethanol and water for three times to obtain the magnetic polymer microspheres with the particle size of 5 microns.
The morphology of the magnetic polymer microspheres obtained in this example was characterized.
Fig. 2 is a scanning electron microscope image of the magnetic polymer microsphere obtained in this embodiment, and it can be seen from the image that the magnetic polymer microsphere obtained in this embodiment has good particle uniformity and small particle size CV.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the magnetic polymer microspheres is characterized by comprising the following steps of:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, and heating to obtain the magnetic nanoparticles;
dissolving the monodisperse polymer microspheres in poor solvent α 1 to obtain a mixture A;
dissolving the magnetic nanoparticles in a good solvent β to obtain a mixture B;
mixing the mixture A and the mixture B, and deswelling the mixture with an undesirable organic solvent α 2 after reaction to obtain the magnetic polymer microsphere;
wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-200: 1.
2. The method for preparing the magnetic polymer microspheres of claim 1, wherein the volume ratio of the poor solvent α 1 to the good solvent β is 1: 1-100: 1.
3. The method for preparing magnetic microspheres according to claim 1, wherein the poor solvent α 1 and the poor solvent α 2 are each independently selected from at least one of ethanol, methanol, isopropanol, ethanol, ethylene glycol, propanol, n-octanol, undecanol, isobutanol, and n-propanol.
4. The method for preparing magnetic microspheres according to claim 1, wherein the good solvent β is at least one selected from the group consisting of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, 1, 2-dichloroethane, and trichloroethane.
5. The method for preparing magnetic polymer microspheres according to any one of claims 1 to 4, wherein the mass ratio of the monodisperse polymer microspheres to the magnetic nanoparticles is 10: 1-10000: 1.
6. the method for preparing magnetic polymer microspheres according to any one of claims 1 to 4, wherein the magnetic nanoparticles have a particle size of 1nm to 100 nm.
7. The method for preparing magnetic polymer microspheres according to any one of claims 1 to 4, wherein the microspheres are selected from at least one of polystyrene-based microspheres, polymethyl methacrylate microspheres, agarose microspheres, polystyrene-divinylbenzene microspheres, and methyl methacrylate-glycerol methacrylate microspheres.
8. The method of any one of claims 1 to 4, wherein the monodisperse polymer microsphere has a particle size of 0.1 μm to 1000 μm.
9. The method for preparing magnetic polymer microspheres according to any one of claims 1 to 4, wherein the step of mixing and heating long-chain fatty acids, medium-short-chain fatty acids and iron long-chain fatty acids to obtain the magnetic nanoparticles comprises:
mixing long-chain fatty acid, medium-short chain fatty acid and long-chain fatty acid iron, heating to 200-400 ℃, and reacting for 1-12 h;
the hydrocarbon chain length X of the long-chain fatty acid1Satisfies the following conditions: x is not less than 131≤40；
The hydrocarbon chain length X of the medium-short chain fatty acid2Satisfies the following conditions: x is not less than 32≤12；
The volume ratio of the long-chain fatty acid to the medium-short-chain fatty acid is 1: 1-100: 1.
10. The magnetic polymer microspheres prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010210863.7A CN111359551B (en) | 2020-03-24 | 2020-03-24 | Magnetic polymer microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010210863.7A CN111359551B (en) | 2020-03-24 | 2020-03-24 | Magnetic polymer microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111359551A true CN111359551A (en) | 2020-07-03 |
| CN111359551B CN111359551B (en) | 2022-04-26 |
Family
ID=71198870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010210863.7A Active CN111359551B (en) | 2020-03-24 | 2020-03-24 | Magnetic polymer microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111359551B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012312A (en) * | 2007-02-08 | 2007-08-08 | 上海交通大学 | Method of preparing multifunctional macromolecule-inorganic composite microsphere |
| CN102049225A (en) * | 2009-10-30 | 2011-05-11 | 北京大学深圳研究生院 | Method for preparing superparamagnetic polymer microspheres |
| GB201209681D0 (en) * | 2012-05-31 | 2012-07-18 | Univ Dublin | Microparticles and a device and method for the synthesis of microparticles |
| CN103143042A (en) * | 2013-02-04 | 2013-06-12 | 厦门大学 | Superpara magnetism polymeric microsphere magnetic resonance imaging (MRI) contrast agent and preparation method thereof |
| CN103153348A (en) * | 2010-08-05 | 2013-06-12 | 韩华石油化学株式会社 | Preparation of extremely small and uniform sized, iron oxide-based paramagnetic or pseudo-paramagnetic nanoparticles and mri t1 contrast agents using the same |
-
2020
- 2020-03-24 CN CN202010210863.7A patent/CN111359551B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012312A (en) * | 2007-02-08 | 2007-08-08 | 上海交通大学 | Method of preparing multifunctional macromolecule-inorganic composite microsphere |
| CN102049225A (en) * | 2009-10-30 | 2011-05-11 | 北京大学深圳研究生院 | Method for preparing superparamagnetic polymer microspheres |
| CN103153348A (en) * | 2010-08-05 | 2013-06-12 | 韩华石油化学株式会社 | Preparation of extremely small and uniform sized, iron oxide-based paramagnetic or pseudo-paramagnetic nanoparticles and mri t1 contrast agents using the same |
| GB201209681D0 (en) * | 2012-05-31 | 2012-07-18 | Univ Dublin | Microparticles and a device and method for the synthesis of microparticles |
| CN103143042A (en) * | 2013-02-04 | 2013-06-12 | 厦门大学 | Superpara magnetism polymeric microsphere magnetic resonance imaging (MRI) contrast agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TING-HAO CHUNG等: "《Preparation of styrene-based, magnetic polymer microspheres by a swelling and penetration process》", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
| 张凯等: "《磁性高分子微球的制备及表征技术》", 《宇航材料工艺》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111359551B (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107299417B (en) | A kind of WO3/ZnWO4The preparation method and products thereof of composite micro-nano rice fiber | |
| Si et al. | Preparation and characterization of bio-compatible Fe3O4@ Polydopamine spheres with core/shell nanostructure | |
| WO2019119568A1 (en) | Magnetic polymer adsorption material, preparation method therefor and application thereof | |
| Chen et al. | Magnetic electrospun fluorescent polyvinylpyrrolidone nanocomposite fibers | |
| Gao et al. | Research progress of poly (methyl methacrylate) microspheres: preparation, functionalization and application | |
| JP5353004B2 (en) | Method for producing spherical ferrite nanoparticles | |
| CN111426659A (en) | Magnetic fluorescent coding microsphere and preparation method thereof | |
| CN111285951B (en) | Lipase/polyion liquid-styrene microsphere/hydrogel catalytic material and preparation method and application thereof | |
| CN113336215A (en) | Preparation method and application of monodisperse hydrothermal carbon spheres | |
| CN108376608B (en) | Magnetic nano particle and application thereof in preparing magnetic solid phase carrier | |
| Chen et al. | Immobilization of penicillin G acylase on paramagnetic polymer microspheres with epoxy groups | |
| Ramesh et al. | Facile synthesis of poly (benzylamine) brushes stabilized silver nanoparticle catalyst for the abatement of environmental pollutant methylene blue | |
| CN111359551B (en) | Magnetic polymer microsphere and preparation method thereof | |
| CN111599588B (en) | Center-radial filling type composite superparamagnetic microsphere and preparation method and application thereof | |
| Liu et al. | Preparation and characterization of superparamagnetic functional polymeric microparticles | |
| Omer-Mizrahi et al. | Synthesis and characterization of magnetic and non-magnetic core–shell polyepoxide micrometer-sized particles of narrow size distribution | |
| CN111533917A (en) | High-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material and preparation method thereof | |
| Liu et al. | A novel CoFe2O4/polyacrylate nanocomposite prepared via an in situ polymerization in emulsion system | |
| CN106867021B (en) | Preparation method of magnetic porous polymer microspheres | |
| Lu et al. | Synthesis and characterization of magnetic polymer microspheres with a core–shell structure | |
| CN112279960B (en) | Preparation method of hydroxyl-containing polydehydroabietate microspheres | |
| Zhou et al. | Direct continuous synthesis of macroRAFT-grafted Fe3O4 nanoclusters for the preparation of magnetic nanocomposites | |
| CN108788181B (en) | Method for synthesizing core-shell structure carbon-coated gold nanoparticles with regular spherical morphology | |
| CN112724305A (en) | Monodisperse quantum dot coded magnetic microspheres | |
| CN113000851A (en) | Method for preparing superparamagnetic nano-iron with controllable particle size by using microchannel reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |