CN114887559B - Preparation method of magnetic microsphere coated by poly (amino ester) with carboxyl group - Google Patents
Preparation method of magnetic microsphere coated by poly (amino ester) with carboxyl group Download PDFInfo
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Abstract
The invention discloses a preparation method of a magnetic microsphere coated by poly (amino ester) carboxyl, which comprises the following steps: firstly preparing an aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by a seed swelling method, then generating magnetic ferroferric oxide nano particles in situ in the porous microsphere by an in-situ generation method to obtain a porous magnetic microsphere, and finally polymerizing and coating polycarboxy poly (amino ester) on the surface of the porous magnetic microsphere to obtain the polycarboxy poly (amino ester) coated magnetic microsphere. The invention uses a simple multi-carboxyl cross-linked polymer to encapsulate the magnetic microsphere, thus improving the stability of the microsphere, the double bond of the residue on the surface of the microsphere can be polymerized, and the polymer polyacrylic acid or polyethylene glycol is used as an extension chain, thus increasing the binding site on the surface of the microsphere and the anti-protein adsorption performance; the synthesis process of the invention is simple to operate, and can provide a preparation method of a novel magnetic carrier for immunoassay, nucleic acid detection and disease diagnosis.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of a magnetic microsphere coated with poly (amino ester) with multiple carboxyl groups.
Background
The magnetic polymer microsphere has the advantages of large specific surface area, controllable particle size, easy separation, surface modification of various functional groups and the like, is widely focused and widely applied to the biomedical field, and has wide application prospect in the aspects of coding technology, cell separation technology, resonance imaging, drug screening and targeting, disease detection and diagnosis and the like.
The preparation method of the magnetic polymer microsphere mainly comprises an embedding method, a monomer polymerization method, an in-situ precipitation method, a layer-by-layer self-assembly method and the like, wherein the in-situ method is widely used because the particle size of the prepared magnetic microsphere is controllable and the magnetic content is high. The in situ method is a method for preparing the monodisperse superparamagnetic composite microsphere, and a series of commercial products, known as Dynabeads, are developed by using the method. The product has been successfully applied to the fields of microbiology, molecular biology, immunology and the like. The in situ method for preparing the magnetic composite microsphere has a plurality of advantages, but has the defect that the method is difficult to overcome: because the surface of the polymer microsphere must contain specific functional groups, the magnetic inorganic particles are deposited on the surface of the polymer microsphere, so that the surface of the finally prepared composite microsphere is not smooth, and the magnetic material of the magnetic composite microsphere exposes the outermost layer of the magnetic microsphere to cause the magnetic microsphere to be reduced due to the oxidation and the falling of the magnetic material, and meanwhile, the magnetic material has certain biotoxicity, so that the application of the microsphere in biology is limited. The polymer coating can avoid the magnetic particles from contacting with the environment to keep stable, and how to design the functional polymer with the surface easy to coat can improve the application environment is critical.
The patent CN108559028A adds the iron oleate monomer suspension and the initiator suspension into the seed suspension to enable the seeds to grow, stops adding the iron oleate monomer suspension and the initiator suspension after reaching the preset microsphere particle size, heats up for the first time, and continues to react to obtain the iron oleate polymer composite microsphere; adding a carboxyl monomer into a mixed solution of a stabilizer and a solvent to obtain a monomer mixed solution; and adding the monomer mixed solution into the iron oleate polymer composite microsphere for secondary polymerization reaction, and heating for the second time to thermally decompose the iron oleate to obtain the magnetic microsphere. The microsphere prepared by the method has low magnetic content and poor dispersibility.
The patent CN111135804A coats an epoxy monomer, a comonomer, a cross-linking agent and an initiator on the surface of a seed microsphere through a water phase in-situ polymerization method to form a uniform epoxy shell layer, then opens epoxy through a ring-opening reaction of an epoxy group to connect with a carboxyl monomer, and finally connects a third carboxyl to the surface of the microsphere through a substitution reaction to form a tridentate carboxyl. The magnetic core of the method is nano-sized, and the modification method is complex and difficult to control the stability.
Therefore, there is a need to provide a more reliable solution.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a magnetic microsphere coated with poly (amino ester) carboxyl aiming at the defects in the prior art. Aiming at the defects existing in the existing preparation of magnetic polymer microspheres, the invention is based on the development of a preparation method of magnetic polymer microspheres with high magnetic content, narrow particle size distribution, simple process and low cost, and adopts an in-situ polymerization method to grow polycarboxy poly (amino ester) on the surface of the aminated porous magnetic microspheres. The invention provides a new method for coating the surface of the magnetic porous microsphere.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of a magnetic microsphere coated by poly (amino ester) with multiple carboxyl groups comprises the following steps: firstly preparing an aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by a seed swelling method, then generating magnetic ferroferric oxide nano particles in situ inside the aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by an in-situ generation method to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere, and finally polymerizing and coating the surface of the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere with poly (amino ester) in situ to obtain the poly (amino ester) -coated magnetic microsphere.
Preferably, the method comprises the steps of:
1) Preparing monodisperse polystyrene seed microspheres;
2) Preparing amino poly (glycidyl methacrylate-divinylbenzene) porous microspheres by the monodisperse polystyrene seed microspheres prepared in the step 1);
3) Preparing the porous magnetic microsphere of the aminated poly (glycidyl methacrylate-divinylbenzene) by using the porous microsphere of the aminated poly (glycidyl methacrylate-divinylbenzene) prepared in the step 2) through an in-situ generation method;
4) And 3) in-situ polymerizing and coating the poly carboxyl poly (amino ester) on the surface of the porous magnetic microsphere of the amino poly (glycidyl methacrylate-diethylbenzene) prepared in the step 3) to prepare the magnetic microsphere coated with the poly carboxyl poly (amino ester).
Preferably, the step 1) specifically includes:
1-1) dissolving polyvinylpyrrolidone in absolute ethyl alcohol, heating and stirring;
1-2) mixing styrene and azodiisobutyronitrile, performing ultrasonic dispersion, and then mixing with the solution obtained in the step 1-1) for reaction;
and 1-3) centrifuging after the reaction is finished, cleaning a solid product, and drying to obtain the monodisperse polystyrene seed microspheres.
The step 1) specifically comprises the following steps:
1-1) adding polyvinylpyrrolidone and absolute ethyl alcohol into a three-mouth bottle, stirring and dissolving at 70 ℃ and 300 rpm;
1-2) mixing styrene and azodiisobutyronitrile, adding into a three-necked flask after ultrasonic dispersion, mixing with the solution obtained in the step 1-1), and introducing N 2 Reacting for 24 hours for 10min;
1-3) centrifuging at 2000rpm for 3min after the reaction is finished, ultrasonically cleaning the solid product with ethanol for 3 times, and drying overnight to obtain the monodisperse polystyrene seed microspheres.
Preferably, the step 2) specifically includes:
2-1) adding the monodisperse polystyrene seed microspheres prepared in the step 1) into water, performing ultrasonic dispersion, and stirring;
2-2) mixing the aqueous solution of sodium dodecyl sulfate, toluene and dibutyl phthalate, dispersing uniformly, then mixing with the product of the step 2-1), and swelling under stirring;
2-3) mixing benzoyl peroxide and styrene, stirring and dissolving, adding sodium dodecyl sulfate aqueous solution, glycidyl methacrylate and divinylbenzene, dispersing uniformly, adding the obtained mixture into the product obtained in the step 2-2), and swelling;
2-4) adding a polyvinyl alcohol aqueous solution into the product obtained in the step 2-3), introducing nitrogen into the obtained reaction system, and heating for reaction;
2-5) after the reaction is finished, washing and drying the product;
2-6) soaking the product obtained in the step 2-5) in ammonia water for reaction, washing the obtained product to be neutral, and drying to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres.
Preferably, the step 2) specifically includes:
2-1) adding the monodisperse polystyrene seed microspheres prepared in the step 1) into water, performing ultrasonic dispersion, transferring into a three-mouth bottle, and stirring at 300 rpm;
2-2) mixing sodium dodecyl sulfate aqueous solution, toluene and dibutyl phthalate (DBP), dispersing uniformly, adding into the three-mouth bottle, mixing with the product of the step 2-1), and swelling for 24 hours at 30 ℃ under stirring at 300 rpm;
2-3) mixing Benzoyl Peroxide (BPO) with styrene (St), stirring to dissolve, adding sodium dodecyl sulfate aqueous solution (SDS), glycidyl Methacrylate (GMA) and Divinylbenzene (DVB), dispersing uniformly, adding the obtained mixture into the three-mouth bottle, and swelling for 24 hours;
2-4) adding a polyvinyl alcohol aqueous solution into the three-mouth bottle, introducing nitrogen, and heating for reaction;
2-5) after the reaction is finished, centrifugally washing the product for three times by using distilled water and ethanol respectively, then adding the product into tetrahydrofuran solution, washing for 12 hours at 60 ℃, centrifugally washing for three times by using water, and drying;
2-6) soaking the product obtained in the step 2-5) in ammonia water for reaction, washing the obtained product with deionized water to be neutral, and drying to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres.
Preferably, the step 3) specifically includes:
3-1) dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in deionized water, and then adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in the step 2) for reaction;
3-2) separating the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres from the solution after the reaction is finished, and then adding the porous microspheres into ammonia water for reaction;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, and then drying in vacuum to obtain the amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres.
Preferably, the step 3) specifically includes:
3-1) dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in deionized water, and then adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in the step 2) for reaction;
3-2) separating the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres from the solution by using a glass funnel after the reaction is finished, adding the microspheres and deionized water into a three-necked flask, and adding ammonia water into the three-necked flask for reaction;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, and then placing the solid product in a vacuum drying oven for drying to obtain the amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres.
Preferably, the step 4) specifically includes:
4-1) adding the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres prepared in the step 3) into dimethyl sulfoxide solution, and performing ultrasonic dispersion;
4-2) sequentially adding 1, 4-butanediol diacrylate and 6-aminocaproic acid solution, and performing ultrasonic dispersion;
4-3) stirring and heating reaction;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product by using water, and magnetically adsorbing, separating and cleaning to obtain the magnetic microsphere coated by the poly (amino ester).
Preferably, the step 4) specifically includes:
4-1) adding the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres prepared in the step 3) into dimethyl sulfoxide solution, and performing ultrasonic dispersion for 10min;
4-2) sequentially adding 1, 4-butanediol diacrylate and 6-aminocaproic acid solution, and performing ultrasonic dispersion for 10min;
4-3) stirring for 10min, heating to 90 ℃, and reacting for 12 hours;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product for three times by using water, and then dissolving, magnetically adsorbing, separating and cleaning the product for three times by using ethanol to obtain the magnetic microsphere coated by the poly (amino ester).
Preferably, the step 4) specifically includes:
4-1) adding the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres prepared in the step 3) into dimethyl sulfoxide solution, and performing ultrasonic dispersion for 10min;
4-2) adding the trimethylolpropane triacrylate and the 6-aminocaproic acid solution in sequence, and performing ultrasonic dispersion for 10min;
4-3) stirring for 10min, heating to 90 ℃, and reacting for 12 hours;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product for three times by using water, and then dissolving, magnetically adsorbing, separating and cleaning the product for three times by using ethanol to obtain the magnetic microsphere coated by the poly (amino ester).
The beneficial effects of the invention are as follows: the invention provides a scheme different from the design of a general magnetic microsphere, and the magnetic microsphere is encapsulated and coated by using a simple multi-carboxyl cross-linked polymer, so that the stability of the microsphere is improved, double bonds of residues on the surface of the microsphere can be polymerized, and the polymer polyacrylic acid or polyethylene glycol is used as an extension chain, so that the binding site on the surface of the microsphere and the protein adsorption resistance can be improved; the synthesis process of the invention is simple to operate, and can provide a preparation method of a novel magnetic carrier for immunoassay, nucleic acid detection and disease diagnosis.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of a polycarboxy poly (amino ester) -coated magnetic microsphere of the present invention;
FIG. 2 is a scanning electron microscope image of the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microsphere prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the polycarboxy poly (amino ester) -coated magnetic microsphere prepared in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
A preparation method of a magnetic microsphere coated by poly (amino ester) with multiple carboxyl groups comprises the following steps: firstly preparing an aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by a seed swelling method, wherein the polymer porous microsphere has uniform size, a porous structure and a larger specific surface area, then generating magnetic ferroferric oxide nano particles in situ in the aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by an in-situ generation method to obtain an aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere with high magnetic content and magnetic response strength, and finally coating polycarboxy poly (amino ester) on the surface of the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere by in-situ polymerization to obtain the magnetic microsphere coated with the polycarboxy poly (amino ester); as the poly (amino ester) coating increases the stability of the magnetic microsphere, the double bond of the surface residue can be polymerized, and the polymer polyacrylic acid or polyethylene glycol is used as an extension chain, so that the surface binding site and the protein adsorption resistance of the microsphere can be increased.
Referring to FIG. 1, a schematic diagram of the synthetic route of the polycarboxy poly (amino ester) -coated magnetic microsphere is shown.
Specifically, the preparation method of the magnetic microsphere coated by the polycarboxy poly (amino ester) comprises the following steps:
1) Preparing monodisperse polystyrene seed microspheres:
1-1) adding 4g of polyvinylpyrrolidone (PVP) and 400g of absolute ethanol into a 1000ml three-necked flask, and stirring and dissolving at 70 ℃ and 300 rpm;
1-2) mixing 40g of styrene and 0.4g of Azobisisobutyronitrile (AIBN), adding into a small beaker, adding into a three-necked flask after ultrasonic dispersion, mixing with the solution obtained in the step 1-1), and introducing N 2 Reacting for 24 hours for 10min;
1-3) centrifuging the milky white liquid obtained after the reaction is finished at 2000rpm for 3min, ultrasonically cleaning the solid product with ethanol for 3 times, and drying overnight to obtain the monodisperse polystyrene seed microspheres.
2) Preparing amino poly (glycidyl methacrylate-divinylbenzene) porous microspheres:
2-1) adding 10g of the monodisperse polystyrene seed microspheres prepared in the step 1) into 100ml of water, performing ultrasonic dispersion, transferring into a three-necked flask, and stirring at 300 rpm;
2-2) mixing 200ml of 0.375% Sodium Dodecyl Sulfate (SDS) aqueous solution, 20ml of toluene and 10ml of dibutyl phthalate (DBP), uniformly dispersing by using a cell pulverizer, adding into the three-necked flask, mixing with the product of the step 2-1), and swelling for 24 hours at 30 ℃ under stirring at 300 rpm;
2-3) mixing 5g of Benzoyl Peroxide (BPO) with 50ml of styrene (St), stirring and dissolving, adding 300ml of 0.25% sodium dodecyl sulfate aqueous solution, 50ml of Glycidyl Methacrylate (GMA) and 40ml of Divinylbenzene (DVB) to obtain a mixture, dispersing uniformly, adding the obtained mixture into a three-mouth bottle, and swelling at 30 ℃ for 24 hours;
2-4) adding 10ml of 10% polyvinyl alcohol (PVA) aqueous solution into the three-mouth bottle, introducing nitrogen for 10min, heating to 70 ℃ and reacting for 24h;
2-5) after the reaction is finished, centrifugally washing the product for three times by using distilled water and ethanol respectively, then adding the product into tetrahydrofuran solution, washing for 12 hours at 60 ℃, centrifugally washing for three times by using water, and drying;
2-6) soaking the product obtained in the step 2-5) in ammonia water for reaction for 12 hours, washing the obtained product with deionized water to be neutral, and drying to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres.
3) Preparing amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres:
3-1) 21g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 5.9g of ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) was dissolved in 300mL of deionized water, followed by adding 20g of the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in step 2) and reacting at 120rpm for 4 hours to ensure ferrous and ferric (Fe) ions in the solution 2+ /Fe 3+ ) The ions can completely react with amino groups in the pore canal of the resin;
3-2) after the reaction, the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres were separated from the solution using a glass funnel, and then Fe was adsorbed on the surface 2+ /Fe 3+ Adding the microspheres and 20mL of deionized water into a three-necked flask, adding 25mL of ammonia water into the three-necked flask, and reacting for 3h at 80 ℃;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, removing the residual alkaline solution on the surfaces of the microspheres, and then placing the microspheres in a vacuum drying oven for drying to obtain the amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres. Referring to FIG. 2, there is a scanning electron microscope image of the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microsphere prepared in this example.
4) Preparing a polycarboxy poly (amino ester) -coated magnetic microsphere:
4-1) adding 1g of the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microsphere prepared in the step 3) into 100ml of dimethyl sulfoxide (DMSO) solution, and performing ultrasonic dispersion for 10min;
4-2) sequentially adding 2g of 1, 4-butanediol diacrylate and 1.5g of 6-aminocaproic acid solution, and performing ultrasonic dispersion for 10min;
4-3) stirring for 10min, gradually heating to 90 ℃, and reacting for 12 hours;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product for three times by using water, and then dissolving, magnetically adsorbing, separating and cleaning the product for three times by using ethanol to obtain the magnetic microsphere coated by the poly (amino ester) with the carboxyl group.
Referring to fig. 3, a scanning electron microscope image of the polycarboxy poly (amino ester) -coated magnetic microsphere prepared in this example is shown.
Example 2
This embodiment is substantially the same as embodiment 1, except for the following:
3) Preparing amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres:
3-1) 43g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 11.8g of ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) was dissolved in 300mL of deionized water, followed by adding 20g of the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in step 2) and reacting at 120rpm for 4 hours to ensure ferrous and ferric (Fe) ions in the solution 2+ /Fe 3+ ) The ion can completely react with the amino inside the resin pore canalReacting;
3-2) after the reaction, the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres were separated from the solution using a glass funnel, and then Fe was adsorbed on the surface 2+ /Fe 3+ Adding the microspheres and 20mL of deionized water into a three-necked flask, adding 25mL of ammonia water into the three-necked flask, and reacting for 3h at 80 ℃;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, removing the residual alkaline solution on the surfaces of the microspheres, and then placing the microspheres in a vacuum drying oven for drying to obtain the amino poly (glycidyl methacrylate-diethylbenzene) porous magnetic microspheres.
The magnetic content of the prepared magnetic microsphere coated by the polycarboxy poly (amino ester) can be adjusted by adjusting the proportion of ferrous chloride tetrahydrate, ferric chloride hexahydrate and the amination poly (glycidyl methacrylate-divinylbenzene) porous microsphere.
Example 3
This embodiment is substantially the same as embodiment 1, except for the following:
4) Preparing a polycarboxy crosslinked poly (amino ester) -coated magnetic microsphere:
4-1) adding 0.5g of the aminated poly (glycidyl methacrylate-diethylbenzene) porous magnetic microsphere prepared in the step 3) into 100ml of dimethyl sulfoxide (DMSO) solution, and performing ultrasonic dispersion for 10min;
4-2) adding 2g of trimethylolpropane triacrylate and 1.5g of 6-aminocaproic acid solution in sequence, and performing ultrasonic dispersion for 10min;
4-3) stirring for 10min, gradually heating to 90 ℃, and reacting for 12 hours;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product for three times by using water, and then dissolving, magnetically separating and cleaning the product for three times by using ethanol to obtain the magnetic microsphere coated by the surface cross-linked polycarboxy poly (amino ester).
Example 4
The product of example 3 was further modified in this example to give EG-functionalized magnetic microspheres, specifically protected:
1) Placing the surface-crosslinked polycarboxy poly (amino ester) -coated magnetic microsphere obtained in example 3 into an Acrylic Acid (AA) and allyl polyethylene glycol solution (1% Wt);
2) N is led to 2 30min, raising the temperature to 70 ℃;
3) Potassium persulfate KPS (2% relative to AA) was added;
4) And after the reaction is finished, the magnetic microsphere is centrifugally washed for three times by water and is magnetically adsorbed, separated and washed for three times, and the magnetic microsphere with the surface cross-linked carboxyl polymer modified and PEG functionalized is obtained.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (4)
1. A preparation method of a magnetic microsphere coated by poly (amino ester) with multiple carboxyl groups is characterized by comprising the following steps: firstly preparing an aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by a seed swelling method, then generating magnetic ferroferric oxide nano particles in situ inside the aminated poly (glycidyl methacrylate-divinylbenzene) porous microsphere by an in-situ generation method to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere, and finally coating the surface of the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microsphere with poly (amino ester) in situ polymerization to obtain the poly (amino ester) -coated magnetic microsphere;
the method comprises the following steps:
1) Preparing monodisperse polystyrene seed microspheres;
2) Preparing amino poly (glycidyl methacrylate-divinylbenzene) porous microspheres by the monodisperse polystyrene seed microspheres prepared in the step 1);
3) Preparing the amino poly (glycidyl methacrylate-divinylbenzene) porous magnetic microspheres by using the amino poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in the step 2) through an in-situ generation method;
4) In-situ polymerizing and coating the poly carboxyl poly (amino ester) on the surface of the porous magnetic microsphere of the amino poly (glycidyl methacrylate-divinylbenzene) prepared in the step 3) to prepare the magnetic microsphere coated with the poly carboxyl poly (amino ester);
the step 1) specifically comprises the following steps:
1-1) adding polyvinylpyrrolidone and absolute ethyl alcohol into a three-mouth bottle, stirring and dissolving at 70 ℃ and 300 rpm;
1-2) mixing styrene and azodiisobutyronitrile, adding into a three-necked flask after ultrasonic dispersion, mixing with the solution obtained in the step 1-1), and introducing N 2 Reacting for 24 hours for 10min;
1-3) centrifuging at 2000rpm for 3min after the reaction is finished, ultrasonically cleaning a solid product with ethanol for 3 times, and drying overnight to obtain monodisperse polystyrene seed microspheres;
the step 2) specifically comprises the following steps:
2-1) adding the monodisperse polystyrene seed microspheres prepared in the step 1) into water, performing ultrasonic dispersion, and stirring;
2-2) mixing the aqueous solution of sodium dodecyl sulfate, toluene and dibutyl phthalate, dispersing uniformly, then mixing with the product of the step 2-1), and swelling under stirring;
2-3) mixing benzoyl peroxide and styrene, stirring and dissolving, adding sodium dodecyl sulfate aqueous solution, glycidyl methacrylate and divinylbenzene, dispersing uniformly, adding the obtained mixture into the product obtained in the step 2-2), and swelling;
2-4) adding a polyvinyl alcohol aqueous solution into the product obtained in the step 2-3), introducing nitrogen into the obtained reaction system, and heating for reaction;
2-5) after the reaction is finished, washing and drying the product;
2-6) soaking the product obtained in the step 2-5) in ammonia water for reaction, washing the obtained product to be neutral, and drying to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres;
the step 3) specifically comprises the following steps:
3-1) dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in deionized water, and then adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in the step 2) for reaction;
3-2) separating the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres from the solution after the reaction is finished, and then adding the porous microspheres into ammonia water for reaction;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, and then drying in vacuum to obtain the amino poly (glycidyl methacrylate-divinylbenzene) porous magnetic microspheres;
the step 4) specifically comprises the following steps:
4-1) adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microspheres prepared in the step 3) into dimethyl sulfoxide solution, and performing ultrasonic dispersion;
4-2) sequentially adding 1, 4-butanediol diacrylate and 6-aminocaproic acid solution, and performing ultrasonic dispersion;
4-3) stirring and heating reaction;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product by using water, and magnetically adsorbing, separating and cleaning to obtain the magnetic microsphere coated by the poly (amino ester).
2. The method for preparing the polycarboxy poly (amino ester) -coated magnetic microsphere according to claim 1, wherein the step 2) specifically comprises:
2-1) adding the monodisperse polystyrene seed microspheres prepared in the step 1) into water, performing ultrasonic dispersion, transferring into a three-mouth bottle, and stirring at 300 rpm;
2-2) mixing the sodium dodecyl sulfate aqueous solution, toluene and dibutyl phthalate, dispersing uniformly, adding into the three-mouth bottle, mixing with the product of the step 2-1), and swelling for 24 hours at 30 ℃ under stirring at 300 rpm;
2-3) mixing benzoyl peroxide and styrene, stirring and dissolving, adding sodium dodecyl sulfate aqueous solution, glycidyl methacrylate and divinylbenzene, dispersing uniformly, adding the obtained mixture into the three-mouth bottle, and swelling for 24 hours;
2-4) adding a polyvinyl alcohol aqueous solution into the three-mouth bottle, introducing nitrogen, and heating for reaction;
2-5) after the reaction is finished, centrifugally washing the product for three times by using distilled water and ethanol respectively, then adding the product into tetrahydrofuran solution, washing for 12 hours at 60 ℃, centrifugally washing for three times by using water, and drying;
2-6) soaking the product obtained in the step 2-5) in ammonia water for reaction, washing the obtained product with deionized water to be neutral, and drying to obtain the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres.
3. The method for preparing the polycarboxy poly (amino ester) -coated magnetic microsphere according to claim 2, wherein the step 3) specifically comprises:
3-1) dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in deionized water, and then adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres prepared in the step 2) for reaction;
3-2) separating the aminated poly (glycidyl methacrylate-divinylbenzene) porous microspheres from the solution by using a glass funnel after the reaction is finished, adding the microspheres and deionized water into a three-necked flask, and adding ammonia water into the three-necked flask for reaction;
3-3) repeatedly cleaning the solid product with absolute ethyl alcohol and deionized water for a plurality of times after the reaction is finished, and then placing the solid product in a vacuum drying oven for drying to obtain the amino poly (glycidyl methacrylate-divinylbenzene) porous magnetic microspheres.
4. The method for preparing the polycarboxy poly (amino ester) -coated magnetic microsphere according to claim 3, wherein the step 4) specifically comprises:
4-1) adding the aminated poly (glycidyl methacrylate-divinylbenzene) porous magnetic microspheres prepared in the step 3) into dimethyl sulfoxide solution, and performing ultrasonic dispersion for 10min;
4-2) sequentially adding 1, 4-butanediol diacrylate and 6-aminocaproic acid solution, and performing ultrasonic dispersion for 10min;
4-3) stirring for 10min, heating to 90 ℃, and reacting for 12 hours;
after the reaction of 4-4), the product is centrifugally cleaned by water and then dissolved by ethanol for magnetic adsorption separation cleaning;
4-5) adding the product obtained in the step 4-4) into a mixed solution of acrylic acid and allyl polyethylene glycol, and reacting under heating;
and 4-6) after the reaction is finished, centrifugally cleaning the product for three times by using water, and then dissolving, magnetically adsorbing, separating and cleaning the product for three times by using ethanol to obtain the magnetic microsphere coated by the poly (amino ester).
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