CN110739143B - Method for preparing magnetic shell-core microspheres based on distillation precipitation method - Google Patents
Method for preparing magnetic shell-core microspheres based on distillation precipitation method Download PDFInfo
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
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Abstract
The invention relates to a method for preparing magnetic shell-core microspheres based on a distillation precipitation method, which comprises the following steps: 1) Dispersing the seed microspheres in an organic solvent, adding a carboxyl monomer, an initiator and a cross-linking agent, and polymerizing on the surfaces of the seed microspheres by a distillation precipitation polymerization method to form a carboxyl shell layer; 2) And depositing iron salt to form magnetic particles distributed in the fluffy carboxyl shell layer by a chemical coprecipitation method to form the magnetic microspheres. The thickness of the carboxyl shell layer can be adjusted by the amount of the carboxyl monomer added. The invention is characterized in that: the fluffy shell layer is adjustable, and the thickness of the shell layer can be changed along with the change of the PH value; the bulkiness of the carboxyl shell layer can be adjusted by adjusting the pH value.
Description
Technical Field
The invention relates to a preparation method of magnetic polymer microspheres, in particular to a method for preparing magnetic shell-core microspheres based on a distillation precipitation method.
Background
The magnetic field assisted separation technology is a technology for separating and enriching a target object based on magnetophoretic motion of magnetic microspheres under the action of an external magnetic field, has the advantages of high efficiency, rapidness, no pollution, integration of separation and enrichment and the like, and is increasingly widely applied to the fields of life science research such as nucleic acid extraction, gene sequencing, cell separation, immunoassay, immobilized enzyme, chiral separation and the like.
The magnetic microspheres can be prepared by various methods, such as a chemical precipitation method, a monomer polymerization method and the like, but the methods have certain limitations, including the defects of non-uniform particle size, wide particle size distribution, complex preparation process, magnetic leakage and the like. Therefore, the method for simply synthesizing the high-quality magnetic nano particles/microspheres is explored, the application of the synthesized new material in the field of biological medicines is developed, and the method has very important scientific significance and practical value.
The mainstream preparation method of the existing magnetic microsphere with wider application comprises the following steps: (1) Taking carboxyl microspheres as cores, adsorbing a cationic polymer on the surfaces of the carboxyl microspheres, adsorbing magnetic fluid again through the cationic polymer, and forming microspheres with certain magnetic performance after repeated times, see U.S. patent No. 7989065B 2; (2) The porous microspheres are used as cores, and are subjected to treatment to be provided with amino groups, then ferric salts are adsorbed, and then the magnetic particles are formed through coprecipitation by using concentrated ammonia water, so that the porous microspheres are provided with magnetism, see U.S. Pat. No.4654267. The two methods have some defects, such as the particle size of the seed microsphere is not too small, the adsorbed magnetic particles are easy to fall off, the treatment process is complicated, the process route is long, and the like.
Disclosure of Invention
The invention aims to provide a method for preparing magnetic shell-core microspheres based on a distillation precipitation method. The method can avoid the defects of the prior art and has the characteristics of uniform particle size, wide particle size distribution, controllable shell thickness and filling power, and simple and convenient process.
The object of the invention can be achieved by the following measures:
a method for preparing magnetic shell-core microspheres based on a distillation precipitation method comprises the following steps:
1) Dispersing the seed microspheres in an organic solvent, adding a carboxyl monomer, an initiator and a cross-linking agent, and polymerizing on the surfaces of the seed microspheres by a distillation precipitation polymerization method to form a carboxyl shell layer;
2) And depositing iron salt to form magnetic particles distributed in the fluffy carboxyl shell layer by a chemical coprecipitation method to form the magnetic microspheres.
Further, the carboxyl monomer is a monomer with carboxyl, preferably one or more of acrylic acid and methacrylic acid.
Further, the seed microsphere is one or more of polystyrene microsphere, polymethyl methacrylate microsphere, polyglycidyl methacrylate microsphere and silicon oxide microsphere.
Furthermore, the iron salt is ferrous salt and ferric salt, wherein ferrous sulfate and ferrous chloride are preferred as the ferrous salt, and ferric chloride and ferric sulfate are preferred as the ferric salt.
Further, the thickness of the carboxyl shell layer can be adjusted by the amount of the carboxyl monomer added.
Furthermore, the amount of the carboxyl monomer is 0-10 times of that of the seed microsphere.
Furthermore, the bulkiness of the carboxyl shell layer can be adjusted by adjusting the pH value.
Furthermore, the pH value is adjusted within the range of 4-11.
Further, the reaction temperature of distillation precipitation polymerization is 60-90 ℃, and the reaction time is 0.5-5 hours.
Furthermore, the particle size of the seed microsphere is 50nm-20um.
The beneficial effects of the invention are: the magnetic microsphere with the shell-core structure has wide particle size distribution from dozens of nanometers to dozens of micrometers, and the core can be made of polymer or inorganic metal material; the thickness of the shell layer can be adjusted and controlled by changing the feeding amount of the carboxyl monomer; the fluffy degree of the shell layer can be adjusted by adjusting the pH value of the solution; the whole process flow is simple and convenient.
Detailed Description
Example 1:
10g of a polystyrene microsphere (500 nm) solution (10 wt%) was weighed, magnetically separated, supernatant removed, and dispersed in 100ml of an acetonitrile solution, and 5g of acrylic acid, 0.25g of N, N-methylenebisacrylamide, and 0.1g of azobisisobutyronitrile were added. And (3) performing ultrasonic treatment on the whole solution for 5min by using a cell crusher, pouring the solution into a three-neck flask, uniformly stirring, heating to 70 ℃, and reacting for 5 hours to obtain the polystyrene microsphere coated with the carboxyl shell layer.
And (3) carrying out centrifugal washing on the obtained polystyrene microspheres coated with the carboxyl shell layers in a centrifugal mode, washing the polystyrene microspheres for 3 times by using absolute ethyl alcohol and deionized water respectively to obtain the carboxyl polystyrene microspheres with the core-shell structures, and filling the carboxyl polystyrene microspheres into a centrifugal tube for later use.
If the fluffiness of the shell layer is adjusted, an acid solution or an alkali solution can be slowly dripped into the solution, and the pH value is adjusted to be 4-11.
Mixing 0.5mol/L Fe2+ solution and 0.5mol/L Fe3+ solution according to the proportion of 1:2 to 10g of the polystyrene microsphere solution with the core-shell structure (10 wt%), stirring for 3 hours to enable a large amount of iron ions to be adsorbed in the shell layer, slowly dropwise adding concentrated ammonia water, stirring, reacting at room temperature for 2 hours, and enabling the iron ions to be coprecipitated to form 20-50nm magnetic particles to be embedded in the shell layer, thereby obtaining the magnetic polystyrene microsphere with the core-shell structure.
Washing the obtained magnetic polystyrene microspheres by a magnetic separation method, washing the microspheres for three times by using ethanol and deionized water respectively, and filling the microspheres into a centrifugal tube for later use.
Example 2:
10g of a polystyrene microsphere (900 nm) solution (10 wt%) was weighed, magnetically separated, supernatant removed, and dispersed in 100ml of an acetonitrile solution, and 5g of acrylic acid, 0.25g of N, N-methylenebisacrylamide, and 0.1g of azobisisobutyronitrile were added. And (3) performing ultrasonic treatment on the whole solution by using a cell crusher for 5min, pouring the solution into a three-neck flask, uniformly stirring, heating to 70 ℃, and reacting for 5 hours to obtain the polystyrene microsphere coated with a carboxyl shell layer.
And (3) carrying out centrifugal washing on the obtained polystyrene microspheres coated with the carboxyl shell layers in a centrifugal mode, washing the polystyrene microspheres for 3 times by using absolute ethyl alcohol and deionized water respectively to obtain the carboxyl polystyrene microspheres with the core-shell structures, and filling the carboxyl polystyrene microspheres into a centrifugal tube for later use.
If the fluffiness of the shell layer is adjusted, an acid solution or an alkali solution can be slowly dripped into the solution, and the pH value is adjusted within the range of 4-11.
Mixing 0.5mol/L Fe2+ solution and 0.5mol/L Fe3+ solution according to the proportion of 1:2 to 10g of the polystyrene microsphere solution with the core-shell structure (10 wt%), stirring for 3 hours to enable a large amount of iron ions to be adsorbed in the shell layer, slowly dropwise adding concentrated ammonia water, stirring, reacting at room temperature for 2 hours, and enabling the iron ions to be coprecipitated to form 20-50nm magnetic particles to be embedded in the shell layer, thereby obtaining the magnetic polystyrene microsphere with the core-shell structure.
Washing the obtained magnetic polystyrene microspheres by a magnetic separation method, washing the microspheres for three times by using ethanol and deionized water respectively, and filling the microspheres into a centrifugal tube for later use.
Example 3:
after 10g of a polystyrene microsphere (5 um) solution (10 wt%) was weighed, after magnetic separation, the supernatant was removed and dispersed in 100ml of an acetonitrile solution, and then 10g of methacrylic acid, 0.5g of divinylbenzene and 0.2g of azobisisobutyronitrile were added. And (3) performing ultrasonic treatment on the whole solution for 5min by using a cell crusher, pouring the solution into a three-neck flask, uniformly stirring, heating to 70 ℃, and reacting for 5 hours to obtain the polystyrene microsphere coated with the carboxyl shell layer.
And (3) centrifugally washing the obtained polystyrene microspheres coated with the carboxyl shell layer in a centrifugal mode, washing the polystyrene microspheres for 3 times by using absolute ethyl alcohol and deionized water respectively to obtain the carboxyl polystyrene microspheres with the core-shell structure, and filling the carboxyl polystyrene microspheres into a centrifugal tube for later use.
If the fluffiness of the shell layer is adjusted, an acid solution or an alkali solution can be slowly dripped into the solution, and the pH value is adjusted to be 4-11.
Mixing 0.5mol/L Fe2+ solution and 0.5mol/L Fe3+ solution according to the proportion of 1:2 to 10g of the polystyrene microsphere solution with the core-shell structure (10 wt%), stirring for 3 hours to enable a large amount of iron ions to be adsorbed in the shell layer, slowly dropwise adding concentrated ammonia water, stirring, reacting at room temperature for 2 hours, and enabling the iron ions to be coprecipitated to form 20-50nm magnetic particles to be embedded in the shell layer, thereby obtaining the magnetic polystyrene microsphere with the core-shell structure.
Washing the obtained magnetic polystyrene microspheres by a magnetic separation method, washing the microspheres for three times by using ethanol and deionized water respectively, and filling the microspheres into a centrifugal tube for later use.
Example 4:
after 10g of a polystyrene microsphere (10 μm) solution (10 wt%) was weighed out and subjected to magnetic separation, the supernatant was removed and dispersed in 100ml of an acetonitrile solution, and 10g of methacrylic acid, 0.5g of divinylbenzene and 0.2g of azobisisobutyronitrile were added thereto. And (3) performing ultrasonic treatment on the whole solution for 5min by using a cell crusher, pouring the solution into a three-neck flask, uniformly stirring, heating to 80 ℃, and reacting for 3 hours to obtain the polystyrene microsphere coated with the carboxyl shell layer.
And (3) carrying out centrifugal washing on the obtained polystyrene microspheres coated with the carboxyl shell layers in a centrifugal mode, washing the polystyrene microspheres for 3 times by using absolute ethyl alcohol and deionized water respectively to obtain the carboxyl polystyrene microspheres with the core-shell structures, and filling the carboxyl polystyrene microspheres into a centrifugal tube for later use.
If the fluffiness of the shell layer is adjusted, an acid solution or an alkali solution can be slowly dripped into the solution, and the pH value is adjusted within the range of 4-11.
Mixing 0.5mol/L Fe2+ solution and 0.5mol/L Fe3+ solution according to the proportion of 1:2 to 10g of the polystyrene microsphere solution with the core-shell structure (10 wt%), stirring for 3 hours to enable a large amount of iron ions to be adsorbed in the shell layer, slowly dropwise adding concentrated ammonia water, stirring, reacting at room temperature for 2 hours, and enabling the iron ions to be coprecipitated to form 20-50nm magnetic particles to be embedded in the shell layer, thereby obtaining the magnetic polystyrene microsphere with the core-shell structure.
And washing the obtained magnetic polystyrene microspheres by a magnetic separation method, washing the microspheres with ethanol and deionized water for three times respectively, and filling the microspheres into a centrifugal tube for later use.
Example 5:
10g of a polystyrene microsphere (20. Mu.m) solution (10 wt%) was weighed, magnetically separated, supernatant was removed, and the solution was dispersed in 100ml of an acetonitrile solution, and 15g of acrylic acid, 0.75g of divinylbenzene and 0.3g of azobisisobutyronitrile were added. And (3) performing ultrasonic treatment on the whole solution for 5min by using a cell crusher, pouring the solution into a three-neck flask, uniformly stirring, heating to 70 ℃, and reacting for 5 hours to obtain the polystyrene microsphere coated with the carboxyl shell layer.
And (3) centrifugally washing the obtained polystyrene microspheres coated with the carboxyl shell layer in a centrifugal mode, washing the polystyrene microspheres for 3 times by using absolute ethyl alcohol and deionized water respectively to obtain the carboxyl polystyrene microspheres with the core-shell structure, and filling the carboxyl polystyrene microspheres into a centrifugal tube for later use.
If the fluffiness of the shell layer is adjusted, an acid solution or an alkali solution can be slowly dripped into the solution, and the pH value is adjusted within the range of 4-11.
Mixing 0.5mol/L Fe2+ solution and 0.5mol/L Fe3+ solution according to the proportion of 1:2, adding the mixture into 10g of the polystyrene microsphere solution (10 wt%) with the core-shell structure in a volume ratio, stirring for 3 hours to enable a large amount of iron ions to be adsorbed in the shell layer, slowly dropwise adding concentrated ammonia water, stirring, reacting at room temperature for 2 hours to enable iron ions to be coprecipitated to form 20-50nm magnetic particles, and embedding the magnetic particles in the shell layer to obtain the magnetic polystyrene microsphere with the core-shell structure.
Washing the obtained magnetic polystyrene microspheres by a magnetic separation method, washing the microspheres for three times by using ethanol and deionized water respectively, and filling the microspheres into a centrifugal tube for later use.
Compared with the prior art, the magnetic shell-core microspheres prepared in the examples 1-5 have the characteristics of uniform particle size, wide particle size distribution, controllable magnetic property and the like, and meanwhile, the shell thickness and the filling power of the microspheres are controllable, and the preparation process is simple and convenient.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
Claims (7)
1. A method for preparing magnetic shell-core microspheres based on a distillation precipitation method is characterized by comprising the following steps: the method comprises the following steps:
1) Dispersing seed microspheres in an organic solvent, adding a carboxyl monomer, an initiator and a cross-linking agent, and polymerizing on the surfaces of the seed microspheres by a distillation precipitation polymerization method to form a carboxyl shell layer;
the filling power of the carboxyl shell layer can be adjusted by adjusting the pH value, wherein the pH value is adjusted by slowly dripping an acid solution or an alkali solution into the solution, and the adjustment range of the pH value is 4-11;
2) Depositing iron salt to form magnetic particles distributed in a fluffy carboxyl shell layer by a chemical coprecipitation method to form magnetic microspheres;
the seed microsphere is one or more of polystyrene microsphere, polymethyl methacrylate microsphere, polyglycidyl methacrylate microsphere and silicon oxide microsphere.
2. The method for preparing the magnetic shell-core microsphere based on the distillation precipitation method according to claim 1, which is characterized in that: the carboxyl monomer is one or more of acrylic acid and methacrylic acid.
3. The method for preparing magnetic shell-core microspheres based on the distillation precipitation method according to claim 1, wherein the method comprises the following steps: the iron salt is ferrous sulfate, ferrous chloride, ferric chloride or ferric sulfate.
4. The method for preparing magnetic shell-core microspheres based on the distillation precipitation method according to claim 3, wherein the method comprises the following steps: the thickness of the carboxyl shell layer can be adjusted by the amount of the carboxyl monomer added.
5. The method for preparing magnetic shell-core microspheres based on the distillation precipitation method according to claim 4, wherein the method comprises the following steps: the amount of the carboxyl monomer is 0-10 times of that of the seed microsphere.
6. The method for preparing the magnetic shell-core microsphere based on the distillation precipitation method according to claim 1, which is characterized in that: the reaction temperature of the distillation precipitation polymerization is 60-90 ℃, and the reaction time is 0.5-5 hours.
7. The method for preparing the magnetic shell-core microsphere based on the distillation precipitation method according to claim 1, which is characterized in that: the particle size of the seed microsphere is 50nm-20um.
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