CN110739143A - 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
- Publication number
- CN110739143A CN110739143A CN201810791835.1A CN201810791835A CN110739143A CN 110739143 A CN110739143 A CN 110739143A CN 201810791835 A CN201810791835 A CN 201810791835A CN 110739143 A CN110739143 A CN 110739143A
- Authority
- CN
- China
- Prior art keywords
- microspheres
- carboxyl
- core
- shell
- distillation precipitation
- 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
Classifications
-
- 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
-
- 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
- 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
- H01F1/0063—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use in a non-magnetic matrix, e.g. granular solids
Abstract
The invention relates to methods for preparing magnetic shell-core microspheres based on a distillation precipitation method, which comprises the steps of 1) dispersing seed microspheres in an organic solvent, then 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) depositing an iron salt by a chemical coprecipitation method to form magnetic particles distributed in a fluffy carboxyl shell layer to form the magnetic microspheres, wherein the thickness of the carboxyl shell layer can be adjusted by the amount of the added carboxyl monomer.
Description
Technical Field
The invention relates to a preparation method of magnetic polymer microspheres, in particular to methods 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, capability of collecting and separating and enriching bodies and the like, and is increasingly applied to 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 a plurality of methods, such as a chemical precipitation method, a monomer polymerization method and the like, but the methods have definite limitations, including the defects of uneven particle size , wide particle size distribution, complex preparation process, magnetic leakage and the like.
The conventional mainstream preparation method of the magnetic microsphere with the application of comprises the following steps of (1) taking the carboxyl microsphere as a core, adsorbing a cationic polymer on the surface of the carboxyl microsphere, adsorbing magnetic fluid again through the cationic polymer, and forming the microsphere with fixed magnetic property after repeated times, which is disclosed in U.S. Pat. No. 7989065B 2, and (2) taking the porous microsphere as a core, carrying out treatment to enable the porous microsphere to carry amino groups, adsorbing iron salts, and then carrying out coprecipitation by using concentrated ammonia water to form magnetic particles, so that the porous microsphere is magnetic, which is disclosed in U.S. Pat. No. 4654267.
Disclosure of Invention
The invention aims to provide methods for preparing magnetic shell-core microspheres based on a distillation precipitation method, which can avoid the defects of the prior art and have the characteristics of uniform particle size, wide particle size distribution, controllable shell thickness and fluffiness, and simple and convenient process.
The object of the invention can be achieved by the following measures:
method for preparing magnetic shell-core microsphere based on distillation precipitation method, comprising 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.
In step , the carboxyl monomer is a monomer with carboxyl, preferably or more of acrylic acid and methacrylic acid.
, the seed microsphere is or more of polystyrene microsphere, polymethyl methacrylate microsphere, polyglycidyl methacrylate microsphere and silicon oxide microsphere.
, the iron salt is ferrous salt and ferric salt, the ferrous salt is ferrous sulfate and ferrous chloride, the ferric salt is ferric chloride and ferric sulfate.
Further to step , the thickness of the carboxyl shell may be adjusted by the amount of carboxyl monomer added.
Further , the amount of carboxyl monomer is 0-10 times of the seed microsphere.
Further , the bulk of the carboxyl shell may be adjusted by adjusting the pH.
Further , the pH is adjusted to 4-11.
, the reaction temperature of distillation precipitation polymerization is 60-90 deg.C, and the reaction time is 0.5-5 hr.
And , the particle size of the seed microsphere is 50nm-20 um.
The invention has the beneficial effects that: 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) 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 weight ratio 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 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 weight ratio 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 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 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 weight ratio 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) 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 weight ratio 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 5:
after 10g of a polystyrene microsphere (20 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 15g of acrylic acid, 0.75g of divinylbenzene and 0.3g 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 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 weight ratio 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.
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.
It will be apparent to those skilled in the art that many changes and modifications can be made without departing from the inventive concept herein, which is intended to be limited only to .
Claims (10)
1, methods for preparing magnetic shell-core microspheres based on distillation precipitation method, which is characterized by comprising 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.
2. The method for preparing magnetic shell-core microspheres based on distillation precipitation as claimed in claim 1, wherein the carboxyl monomer is a carboxyl-containing monomer, preferably or more of acrylic acid and methacrylic acid.
3. The method for preparing magnetic shell-core microspheres based on distillation precipitation method according to claim 2, wherein the seed microspheres are or more of polystyrene microspheres, polymethyl methacrylate microspheres, polyglycidyl methacrylate microspheres, and silica microspheres.
4. The method for preparing magnetic shell-core microspheres based on distillation precipitation method according to claim 3, wherein the iron salt is selected from ferrous salts and ferric salts, the ferrous salts are preferably ferrous sulfate and ferrous chloride, and the ferric salts are preferably ferric chloride and ferric sulfate.
5. The method for preparing magnetic shell-core microsphere based on distillation precipitation method as claimed in claim 4, wherein the thickness of the carboxyl shell layer can be adjusted by the amount of carboxyl monomer added.
6. The method for preparing magnetic shell-core microspheres based on distillation precipitation as claimed in claim 5, wherein the amount of the carboxyl monomer is 0-10 times of that of the seed microspheres.
7. The method for preparing magnetic shell-core microsphere based on distillation precipitation method as claimed in claim 6, wherein the bulkiness of the carboxyl shell layer can be adjusted by adjusting pH.
8. The method for preparing magnetic shell-core microspheres based on distillation precipitation as claimed in claim 7, wherein the pH is adjusted in the range of 4-11.
9. The method of claim 1, wherein the temperature of the distillation precipitation polymerization is 60-90 deg.C and the time is 0.5-5 hours.
10. The method for preparing magnetic shell-core microspheres based on distillation precipitation method according to claim 1, wherein the seed microspheres have a particle size of 50nm-20 um.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810791835.1A CN110739143B (en) | 2018-07-18 | 2018-07-18 | Method for preparing magnetic shell-core microspheres based on distillation precipitation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810791835.1A CN110739143B (en) | 2018-07-18 | 2018-07-18 | Method for preparing magnetic shell-core microspheres based on distillation precipitation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110739143A true CN110739143A (en) | 2020-01-31 |
CN110739143B CN110739143B (en) | 2022-10-28 |
Family
ID=69234956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810791835.1A Active CN110739143B (en) | 2018-07-18 | 2018-07-18 | Method for preparing magnetic shell-core microspheres based on distillation precipitation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110739143B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116272702A (en) * | 2022-11-22 | 2023-06-23 | 广州蔚捷生物医药科技有限公司 | Biological nanometer microsphere and preparation method and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654267A (en) * | 1982-04-23 | 1987-03-31 | Sintef | Magnetic polymer particles and process for the preparation thereof |
CN101004414A (en) * | 2007-01-16 | 2007-07-25 | 华东理工大学 | Magnetic microspheres of macromolecule, and synthesizing preparation method in situ |
CN102029133A (en) * | 2009-09-29 | 2011-04-27 | 北京万德高科技发展有限公司 | Porous polymer microsphere and functional composite polymer microsphere as well as preparation method and application thereof |
CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
CN103588920A (en) * | 2013-10-31 | 2014-02-19 | 天津工业大学 | Novel preparation method for monodisperse porous polymer nano microcapsule |
CN104448131A (en) * | 2014-11-11 | 2015-03-25 | 南京工业大学 | Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent |
CN107115830A (en) * | 2017-03-28 | 2017-09-01 | 南京林业大学 | A kind of method that polymer microsphere is prepared based on high-pressure electrostatic ultrasonic atomizatio |
CN108046277A (en) * | 2017-12-28 | 2018-05-18 | 苏州纳微科技有限公司 | A kind of preparation method of micron order hollow magnetic silicon dioxide microsphere |
CN108192007A (en) * | 2017-12-28 | 2018-06-22 | 苏州英芮诚生化科技有限公司 | A kind of carboxy-functionalized polyurethane coated magnetic microballoon and preparation method thereof |
-
2018
- 2018-07-18 CN CN201810791835.1A patent/CN110739143B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4654267A (en) * | 1982-04-23 | 1987-03-31 | Sintef | Magnetic polymer particles and process for the preparation thereof |
CN101004414A (en) * | 2007-01-16 | 2007-07-25 | 华东理工大学 | Magnetic microspheres of macromolecule, and synthesizing preparation method in situ |
CN102029133A (en) * | 2009-09-29 | 2011-04-27 | 北京万德高科技发展有限公司 | Porous polymer microsphere and functional composite polymer microsphere as well as preparation method and application thereof |
CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epoxy chloropropane cross-linked chitosan microspheres |
CN103588920A (en) * | 2013-10-31 | 2014-02-19 | 天津工业大学 | Novel preparation method for monodisperse porous polymer nano microcapsule |
CN104448131A (en) * | 2014-11-11 | 2015-03-25 | 南京工业大学 | Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent |
CN107115830A (en) * | 2017-03-28 | 2017-09-01 | 南京林业大学 | A kind of method that polymer microsphere is prepared based on high-pressure electrostatic ultrasonic atomizatio |
CN108046277A (en) * | 2017-12-28 | 2018-05-18 | 苏州纳微科技有限公司 | A kind of preparation method of micron order hollow magnetic silicon dioxide microsphere |
CN108192007A (en) * | 2017-12-28 | 2018-06-22 | 苏州英芮诚生化科技有限公司 | A kind of carboxy-functionalized polyurethane coated magnetic microballoon and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
刘广宇: "亲水性聚合物微球、无机/聚合物杂化微球和空心微球的合成研究", 《万方》 * |
杨明等: "《药剂学》", 31 August 2014, 中国医药科技出版社 * |
赵睿等: "碱溶法制备高孔隙度多孔微球", 《色谱》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116272702A (en) * | 2022-11-22 | 2023-06-23 | 广州蔚捷生物医药科技有限公司 | Biological nanometer microsphere and preparation method and application thereof |
CN116272702B (en) * | 2022-11-22 | 2023-09-26 | 广州蔚捷生物医药科技有限公司 | Biological nanometer microsphere and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110739143B (en) | 2022-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108467461B (en) | Preparation method of surface carboxyl core-shell superparamagnetic microspheres | |
CN102142310B (en) | Preparing method of nano-magnetic polymer composite microsphere | |
Feyen et al. | Synthesis of structurally stable colloidal composites as magnetically recyclable acid catalysts | |
CN1186377C (en) | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof | |
CN101250313B (en) | Nano-particle compound and preparation method thereof | |
CN101220187A (en) | Magnetic composite microsphere with nucleocapsid structure and method for producing the same | |
CN111375360B (en) | Preparation method of magnetic microspheres with uniform particle size | |
CN111393574B (en) | Magnetic microsphere with functional groups on surface and preparation method and application thereof | |
CN103272544B (en) | Core-shell type raspberry-shaped intelligent composite microsphere sensitive to both temperature and pH, and preparation method thereof | |
CN109985584B (en) | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres | |
CN108654528B (en) | Magnetic polymer core-shell structure microsphere and preparation method and application thereof | |
CN110734524A (en) | Preparation method of cationic polymer modified magnetic shell-core microsphere | |
CN105688856A (en) | Decorating method of porous carbon microsphere quaternization | |
CN114591726B (en) | Method for preparing stable monodisperse crosslinked polystyrene magnetic microspheres | |
CN112175150A (en) | Novel preparation method of functionalized porous magnetic microspheres | |
CN110739143B (en) | Method for preparing magnetic shell-core microspheres based on distillation precipitation method | |
CN103432971A (en) | Preparation method of dissymmetric hollow microspheres based on polymer template particles | |
CN101386671B (en) | Method for preparing environmental responsibility mesoporous silicon sphere | |
CN106430222A (en) | Nanosilicon dioxide pellet and preparing method thereof | |
CN103396505A (en) | Preparation method of pure cationic nanosphere | |
JP4548598B2 (en) | Magnetic particle, method for producing the same, and carrier for biochemistry | |
CN107042093B (en) | A kind of preparation method of the big ball adsorbent material of composite magnetic hydroxyapatite | |
CN107915801B (en) | Preparation method of raspberry type pH value/temperature sensitive polymer microcapsule | |
CN111116851A (en) | Preparation method of polyquaternium magnetic microsphere with core-shell structure | |
CN104558353A (en) | Method for preparing magnetic polymer microspheres by multiple emulsion method |
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 |