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
- Publication number
- CN110739143B CN110739143B CN201810791835.1A CN201810791835A CN110739143B CN 110739143 B CN110739143 B CN 110739143B CN 201810791835 A CN201810791835 A CN 201810791835A CN 110739143 B CN110739143 B CN 110739143B
- Authority
- CN
- China
- Prior art keywords
- carboxyl
- microspheres
- microsphere
- shell
- magnetic
- 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.)
- Active
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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Nanotechnology (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Micro-Capsules (AREA)
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.
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 CN110739143A (en) | 2020-01-31 |
CN110739143B true 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) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO155316C (en) * | 1982-04-23 | 1987-03-11 | Sintef | PROCEDURE FOR MAKING MAGNETIC POLYMER PARTICLES. |
CN101004414A (en) * | 2007-01-16 | 2007-07-25 | 华东理工大学 | Magnetic microspheres of macromolecule, and synthesizing preparation method in situ |
CN102029133B (en) * | 2009-09-29 | 2013-03-27 | 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 |
CN103588920B (en) * | 2013-10-31 | 2017-01-25 | 天津工业大学 | Novel preparation method for monodisperse porous polymer nano microcapsule |
CN104448131B (en) * | 2014-11-11 | 2016-08-31 | 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 |
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 |
CN108046277B (en) * | 2017-12-28 | 2021-04-02 | 苏州纳微科技股份有限公司 | Preparation method of micron-sized hollow magnetic silica microspheres |
-
2018
- 2018-07-18 CN CN201810791835.1A patent/CN110739143B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Non-Patent Citations (1)
Title |
---|
碱溶法制备高孔隙度多孔微球;赵睿等;《色谱》;20051231;第23卷(第6期);第616-618页 * |
Also Published As
Publication number | Publication date |
---|---|
CN110739143A (en) | 2020-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Feyen et al. | Synthesis of structurally stable colloidal composites as magnetically recyclable acid catalysts | |
CN102142310B (en) | Preparation method of nano magnetic polymer composite microspheres | |
CN111393574B (en) | Magnetic microsphere with functional groups on surface and preparation method and application 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 | |
CN102500296A (en) | Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers | |
CN102391603B (en) | Preparation method of novel magnetism macromolecule hydrogel | |
CN103304753A (en) | Preparation method of epoxy functional core-shell structure magnetic polymer microsphere | |
US20200338523A1 (en) | Magnetic strong base anion exchange resin with high mechanical strength, and preparation method thereof | |
CN103012828A (en) | Polymer ferric oxide microsphere preparation method | |
CN100531973C (en) | Method for preparing cubic copper particles | |
CN103848456A (en) | Preparation method of tin dioxide micro-nano particles with hollow structures | |
CN110739143B (en) | Method for preparing magnetic shell-core microspheres based on distillation precipitation method | |
CN108654528B (en) | Magnetic polymer core-shell structure microsphere and preparation method and application thereof | |
CN107175086A (en) | The preparation method of ion blotting magnetite gathering material | |
CN114591726B (en) | Method for preparing stable monodisperse crosslinked polystyrene magnetic microspheres | |
CN110734524A (en) | Preparation method of cationic polymer modified magnetic shell-core microsphere | |
CN101386671B (en) | Method for preparing environmental responsibility mesoporous silicon sphere | |
CN112175150A (en) | Novel preparation method of functionalized porous magnetic microspheres | |
CN103396505A (en) | Preparation method of pure cationic nanosphere | |
CN107042093B (en) | A kind of preparation method of the big ball adsorbent material of composite magnetic hydroxyapatite | |
CN104558353A (en) | Method for preparing magnetic polymer microspheres by multiple emulsion method | |
CN110732296B (en) | Preparation method of magnetic microspheres with fluffy shell layers | |
CN103272543A (en) | Method for preparing hollow silicon ball by self-templating method | |
CN112250076B (en) | Preparation method of nano calcium silicate hydrate |
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 |