CN116444730A - Preparation method of porous magnetic polymer microsphere - Google Patents

Preparation method of porous magnetic polymer microsphere Download PDF

Info

Publication number
CN116444730A
CN116444730A CN202310446440.9A CN202310446440A CN116444730A CN 116444730 A CN116444730 A CN 116444730A CN 202310446440 A CN202310446440 A CN 202310446440A CN 116444730 A CN116444730 A CN 116444730A
Authority
CN
China
Prior art keywords
microspheres
reaction
magnetic
porous
microsphere
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.)
Pending
Application number
CN202310446440.9A
Other languages
Chinese (zh)
Inventor
姜勇
蒋文婕
卜凤杰
张金泉
王志飞
吴地艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southeast University
Original Assignee
Southeast University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Southeast University filed Critical Southeast University
Priority to CN202310446440.9A priority Critical patent/CN116444730A/en
Publication of CN116444730A publication Critical patent/CN116444730A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a porous magnetThe preparation method of the sexual polymer microsphere comprises the following steps: (1) The polystyrene seed microsphere is swelled in the first step under the action of a swelling agent and a surfactant, swelled in the second step under the action of a functional monomer, an initiator and the surfactant, and the functionalized porous polymer microsphere is prepared; (2) Mixing porous polymer microspheres, an iron source, an alkali source, polyalcohol and a surfactant, and fully absorbing under stirring; (3) And transferring the fully absorbed mixture into a high-pressure reaction kettle, and preparing the magnetic polymer microsphere through a solvothermal method. The invention adopts a solvothermal method to synthesize submicron magnetic Fe on porous polymer microspheres in situ 3 O 4 The nanoclusters can enhance the magnetism of the magnetic polymer microspheres, improve the magnetization intensity of the magnetic polymer microspheres, effectively prevent the aggregation of the magnetic polymer microspheres, improve the dispersibility of the magnetic polymer microspheres and realize the controllability of the particle sizes of the magnetic polymer microspheres; in addition, magnetic Fe 3 O 4 The nanoclusters are mostly grown in the pores of the porous polymer microspheres or in the hollow cavities of the hydrogel hollow microspheres, so that the subsequent surface functionalization modification of the microspheres is facilitated.

Description

Preparation method of porous magnetic polymer microsphere
Technical Field
The invention relates to a preparation method of porous magnetic polymer microspheres.
Background
The magnetic polymer microsphere is a novel functional material formed by compounding magnetic particles and a high polymer through a physical or chemical method, and the microsphere with magnetic effect and biocompatibility has wide application prospect in the fields of medicine, biology, environmental protection and the like.
In decades of development in this field, magnetic polymer microspheres with various properties and structures are prepared, and the magnetic polymer microspheres can be classified into the following four types according to microsphere structures: core-shell, inverse core-shell, diffuse and sandwich. The preparation methods of these structural products are three: the first method is to obtain core-shell magnetic polymer microspheres by wrapping magnetic inorganic particles with natural or synthetic polymers, which is an earlier method for preparing the magnetic polymer microspheres; the second method is the most commonly used method at present, which takes inorganic magnetic particles as a mother nucleus and carries out monomer polymerization to prepare magnetic polymer microspheres; and thirdly, a layer of uniform magnetic material is coated on a polymer microsphere mother core, for example, a layer of paramagnetic iron oxide particles is coated on the surface of a polymethyl methacrylate microsphere through physical grinding in patent US7732051, or for example, magnetic nano particles are prepared by in-situ coprecipitation growth on the surface of the polymer microsphere in patent US20170218095, and the magnetic polymer microsphere prepared by the method has low magnetization intensity and high process control difficulty.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of porous magnetic polymer microspheres, which has uniform particle size and high magnetization intensity and is easy to carry out subsequent functionalization modification on the microspheres.
The technical scheme is as follows: the preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) The polystyrene seed microsphere is swelled in the first step under the action of a swelling agent and a surfactant, swelled in the second step under the action of a functional monomer, an initiator and the surfactant, and the functionalized porous polymer microsphere is prepared; the first swelling can make the polymer molecular chain softer, so that the functional monomer can be better dissolved into the molecular chain during the second swelling, and the functional monomer is used for the second chelation reaction with iron ions;
(2) Mixing porous polymer microspheres, an iron source, an alkali source, polyalcohol and a surfactant, fully absorbing under stirring, and capturing the iron source in a reaction system by functional groups on the surfaces of the polymer microspheres to perform chelation reaction;
(3) And (3) transferring the mixture material fully absorbed in the step (2) into a high-pressure reaction kettle, and preparing the magnetic polymer microsphere through a solvothermal method.
Wherein in the step (1), the functional monomer is a monomer with at least two functional groups of amino, carboxyl, epoxy or hydroxyl; the functional groups on the surface of the functionalized porous polymer microsphere are at least two of amino, carboxyl, epoxy or hydroxyl, and the crosslinking degree is 5-25%. The crosslinking degree is improved by adjusting the mass ratio of the crosslinking agent to the monomer, and the higher the molecular weight of the obtained polymer is, the higher the crosslinking degree is, so that the structural strength of the obtained microsphere is higher.
Wherein in the step (2), the absorption temperature is 20-80 ℃ and the absorption time is 0.5-24 h.
Wherein in the step (2), the mass-volume ratio of the porous polymer microsphere, the iron source, the alkali source, the polyol and the surfactant is 1g: 6-10 g: 6-10 g: 3.5-5 g: 80-100 mL.
Wherein the iron source is one or a combination of a plurality of ferric trichloride hexahydrate, ferric trichloride, ferrous chloride tetrahydrate or ferrous sulfate heptahydrate; the polyol is one of ethylene glycol, 1, 2-propylene glycol or glycerol; the alkali source is one of sodium acetate, sodium citrate, ammonium acetate, triethylamine, ammonia water or sodium hydroxide; the surfactant is one of polyacrylic acid, sodium polyacrylate, polyacrylamide or polyethylene glycol.
Wherein in the step (3), magnetic Fe is synthesized in situ on the pores and the surface of the porous polymer microsphere by a solvothermal method 3 O 4 The reaction temperature of the nanoclusters is 150-220 ℃, the temperature rising rate is 50-200 ℃/h, and the reaction time is 6-36 h.
In the step (3), after the reaction is finished, cooling the reaction kettle, taking out the product, magnetically sucking or centrifuging to separate, washing with distilled water for 3-4 times, and dispersing the final product in distilled water.
Wherein in the step (3), the diameter of the magnetic polymer microsphere is 0.8-5 mu m, and the magnetic Fe 3 O 4 The diameter of the nanoclusters is 50-500 nm.
The invention adopts the porous polymer microsphere as the mother nucleus, and the porous polymer microsphere has high specific surface area, low density and high porosity, thereby being capable of fully absorbing iron source, polyalcohol, alkali source and surfactant, greatly improving the magnetic content of the subsequent magnetic polymer microsphere and magnetic Fe 3 O 4 The nanoclusters grow mostly in the pores of the porous polymer microspheres, and the surfaces of the microspheres have only a few magnetic Fe 3 O 4 Nanoclusters for convenient post encapsulation; dissolving functional monomer into molecular chain by swelling method, and mixing with iron ionChelating coordination reaction is facilitated for the later in-situ synthesis of magnetic Fe 3 O 4 A nanocluster; the porous polymer microsphere has high rigidity, high mechanical strength and chemical stability, and the higher the crosslinking degree is, the less the polymer microsphere is easy to damage in the solvothermal process.
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Adding a reaction monomer and an initiator into a solvent to perform precipitation polymerization reaction, and obtaining a spherical polymer after the reaction is finished; adding a cross-linking agent or adding the cross-linking agent and a reaction monomer into a reaction system, and carrying out polymerization again to obtain microspheres with core-shell structures after the reaction is finished, wherein the microspheres consist of spherical polymers and cross-linked shell layers coated outside the spherical polymers; centrifugally washing the microsphere with the non-crosslinked core and the crosslinked shell, and removing spherical polymers in the crosslinked shell to obtain the hydrogel hollow microsphere with a cavity structure;
adding monomers into a solvent, then adding an initiator, introducing nitrogen for deoxidization (removing oxygen in the air, wherein the polymerization reaction is initiated by free radicals, the existence of the oxygen can be combined with the free radicals, the reaction rate is greatly reduced, and the yield is reduced), and carrying out reflux precipitation polymerization reaction in the first stage; after the first-stage reaction is finished, adding a mixed monomer (containing a cross-linking agent and a reaction monomer or only containing the cross-linking agent) into the same reaction system, reacting to obtain hydrogel microspheres with non-cross-linked cores and cross-linked shell layers, and then centrifugally washing the hydrogel microspheres with ethanol and water to remove the middle non-cross-linked cores, thereby obtaining hydrogel hollow microspheres, namely the microspheres with internal cavity structures;
(2) Mixing hydrogel hollow microspheres, an iron source, an alkali source, polyalcohol and a surfactant, fully absorbing under stirring, and capturing the iron source in a reaction system by functional groups on the surfaces of the microspheres to perform chelation reaction;
(3) And (3) transferring the mixture material fully absorbed in the step (2) into a high-pressure reaction kettle, and preparing the magnetic polymer microsphere through a solvothermal method.
In the step (1), the solvent is acetonitrile or a mixed solvent of acetonitrile and ethanol, the particle size of the microspheres is controlled according to the addition proportion of the acetonitrile and the ethanol, the ethanol is equivalent to a good solvent, and the particle size of the microspheres is increased by adding the ethanol; the initiator is azodiisobutyronitrile, azodiisovaleronitrile or benzoyl peroxide; the reaction monomer is one or more of acrylic acid, methacrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxyethyl, hydroxypropyl methacrylate, acrylamide, methacrylamide or N-isopropyl acrylamide; the cross-linking agent is divinylbenzene, methylene bisacrylamide and dimethyl glycol ester and other cross-linking agents containing more than two unsaturated ethylenic bonds.
Wherein in the step (2), the absorption temperature is 20-80 ℃ and the absorption time is 0.5-24 h.
In the step (2), the mass-volume ratio of the hydrogel hollow microspheres to the iron source to the alkali source to the polyol to the surfactant is 1g: 6-10 g: 6-10 g: 3.5-5 g: 80-100 mL.
Wherein the iron source is one or a combination of a plurality of ferric trichloride hexahydrate, ferric trichloride, ferrous chloride tetrahydrate or ferrous sulfate heptahydrate; the polyol is one of ethylene glycol, 1, 2-propylene glycol or glycerol; the alkali source is one of sodium acetate, sodium citrate, ammonium acetate, triethylamine, ammonia water or sodium hydroxide; the surfactant is one of polyacrylic acid, sodium polyacrylate, polyacrylamide or polyethylene glycol.
Wherein in the step (3), magnetic Fe is synthesized in situ in the hollow cavities and on the surfaces of the hollow microspheres of the hydrogel by a solvothermal method 3 O 4 The reaction temperature of the nanoclusters is 150-220 ℃, the temperature rising rate is 50-200 ℃/h, and the reaction time is 6-36 h.
In the step (3), after the reaction is finished, cooling the reaction kettle, taking out the product, magnetically sucking or centrifuging to separate, washing with distilled water for 3-4 times, and dispersing the final product in distilled water.
Wherein in the step (3), the diameter of the magnetic polymer microsphere is 0.8-5 mu m, and the magnetic Fe 3 O 4 The diameter of the nanoclusters is 50-500 nm. The magnetic polymer microsphere has a coefficient of variation of about 0.01～0.5。
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the invention adopts a solvothermal method to synthesize submicron magnetic Fe on porous polymer microspheres in situ 3 O 4 The nanoclusters can enhance the magnetism of the magnetic polymer microspheres, improve the magnetization intensity of the magnetic polymer microspheres, effectively prevent the aggregation of the magnetic polymer microspheres, improve the dispersibility of the magnetic polymer microspheres and realize the controllability of the particle sizes of the magnetic polymer microspheres; in addition, magnetic Fe 3 O 4 The nanoclusters are mostly grown in the pores of the porous polymer microspheres or in the hollow cavities of the hydrogel hollow microspheres, so that the subsequent surface functionalization modification of the microspheres is facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of functionalized porous polymer microspheres of example 1;
FIG. 2 is a scanning electron microscope image of hydrogel hollow microspheres of example 2;
FIG. 3 is a scanning electron microscope image of the magnetic polymer microspheres prepared in example 1;
FIG. 4 is a hysteresis regression line of the magnetic polymer microsphere prepared in example 1.
FIG. 5 shows the dispersibility and suspension ability of the magnetic polymer microspheres prepared in example 1 in water.
Detailed Description
Example 1
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Synthesis of functionalized porous polymer microspheres: firstly, adding 30mL of isopropanol and 20mL of distilled water into a 100mL three-neck flask, then adding 0.75g of polyvinylpyrrolidone, 5mL of styrene and 0.10g of azodiisobutyronitrile into the three-neck flask, and heating to 75 ℃ under the protection of nitrogen to react for 12 hours to obtain polystyrene seed microspheres with the particle size of about 1 mu m; 1.2mL of toluene and 3.6mL of dibutyl phthalate are added into 60mL of aqueous solution containing 0.1g of sodium dodecyl sulfate, ultrasonic emulsification is completed, and then 0.2 g of polystyrene seed microsphere is added into the mixture to swell for 12 hours at room temperature; 5mL of methyl methacrylate, 1mL of divinylbenzene, 1mL of glycidyl methacrylate and 0.24g of benzoyl peroxide were added to 60mL of an aqueous solution containing 0.1g of sodium dodecyl sulfate, and the mixture was phacoemulsified; adding the emulsion into the reaction liquid after swelling for 12 hours, and continuing swelling for 6 hours; finally, carrying out polymerization reaction for 16h at 70 ℃ under the protection of nitrogen atmosphere to obtain porous polymer microspheres; hydrolyzing 1g of porous polymer microspheres with 30mL of 5wt% sodium hydroxide aqueous solution at 80 ℃ for 3 hours, washing with distilled water to be neutral after the hydrolysis is finished, and condensing and refluxing with 30mL of 0.2mol/L sulfuric acid aqueous solution at 80 ℃ for 4 hours to obtain functionalized porous polymer microspheres;
(2) Dispersing 1g of functionalized porous polymer microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing the mixture by ultrasonic, and transferring the mixture into a three-neck flask to be slowly stirred for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 10h; and after the product is cooled, magnetically separating, and cleaning the product for 3 to 4 times by pure water to obtain the porous magnetic polymer microsphere.
As can be seen from FIG. 1, the porous magnetic polymer microsphere prepared in example 1 has good dispersibility.
Example 2
(1) Weighing 0.12g of azodiisobutyronitrile, dissolving in 100mL of mixed solvent of acetonitrile and ethanol, adding 6mL of methacrylic acid, introducing nitrogen for 30 minutes for deoxidization, and then immersing in an oil bath at 80-100 ℃ for reaction for 0.5-3 hours; adding a mixed solution composed of 1mL of methacrylic acid and 0.25mL of divinylbenzene into a reaction system after precipitation polymerization reaction, and reacting for 1-3 hours; after the reaction is finished, centrifugally washing the mixture by ethanol and water, and removing non-crosslinked polymethacrylic acid cores to obtain hollow microspheres of poly (divinylbenzene-methacrylic acid);
(2) Dispersing 1g of hollow microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing by ultrasonic, transferring the mixture into a three-neck flask, and slowly stirring the mixture for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 10h; and after the product is cooled, magnetically separating, and cleaning the product for 3 to 4 times by pure water to obtain the porous magnetic polymer microsphere.
The hollow microsphere formed by adopting the precipitation polymerization method has uniform microsphere particle size, and the particle size of the microsphere can be adjusted by adjusting the mass ratio of the reaction monomer in the solvent, so that the formed hydrogel hollow microsphere with a cavity structure inside can be effectively deposited in the hydrogel microsphere.
Example 3
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Synthesis of functionalized porous polymer microspheres: firstly, adding 30mL of isopropanol and 20mL of distilled water into a 100mL three-neck flask, then adding 0.75g of polyvinylpyrrolidone, 5mL of styrene and 0.10g of azodiisobutyronitrile into the three-neck flask, and heating to 75 ℃ under the protection of nitrogen to react for 12 hours to obtain polystyrene seed microspheres with the particle size of about 1 mu m; 1.2mL of toluene and 3.6mL of dibutyl phthalate are added into 60mL of aqueous solution containing 0.1g of sodium dodecyl sulfate, ultrasonic emulsification is completed, and then 0.2 g of polystyrene seed microsphere is added into the mixture to swell for 12 hours at room temperature; 5.5mL of methyl methacrylate, 0.5mL of divinylbenzene, 1mL of glycidyl methacrylate and 0.24g of benzoyl peroxide were added to 60mL of an aqueous solution containing 0.1g of sodium dodecyl sulfate, and the mixture was phacoemulsified; adding the emulsion into the reaction liquid after swelling for 12 hours, and continuing swelling for 6 hours; finally, carrying out polymerization reaction for 16h at 70 ℃ under the protection of nitrogen atmosphere to obtain porous polymer microspheres; hydrolyzing 1g of porous polymer microspheres with 30mL of 5wt% sodium hydroxide aqueous solution at 80 ℃ for 3 hours, washing with distilled water to be neutral after the hydrolysis is finished, and condensing and refluxing with 30mL of 0.2mol/L sulfuric acid aqueous solution at 80 ℃ for 4 hours to obtain functionalized porous polymer microspheres;
(2) Dispersing 1g of functionalized porous polymer microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing the mixture by ultrasonic, and transferring the mixture into a three-neck flask to be slowly stirred for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 8h; and after the product is cooled, magnetically separating, and cleaning the product for 3 to 4 times by pure water to obtain the porous magnetic polymer microsphere.
As is clear from the comparison between example 1 and example 3, the porous polymer microspheres prepared in example 3 have higher crosslinking degree, higher stability and strength at high temperature of 200 ℃ and are not easy to break.
Example 4
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Synthesis of functionalized porous polymer microspheres: firstly, adding 30mL of isopropanol and 20mL of distilled water into a 100mL three-neck flask, then adding 0.75g of polyvinylpyrrolidone, 5mL of styrene and 0.10g of azodiisobutyronitrile into the three-neck flask, and heating to 75 ℃ under the protection of nitrogen to react for 12 hours to obtain polystyrene seed microspheres with the particle size of about 1 mu m; 1.2mL of toluene and 3.6mL of dibutyl phthalate are added into 60mL of aqueous solution containing 0.1g of sodium dodecyl sulfate, ultrasonic emulsification is completed, and then 0.2 g of polystyrene seed microsphere is added into the mixture to swell for 12 hours at room temperature; 5mL of methyl methacrylate, 1mL of divinylbenzene, 1mL of glycidyl methacrylate and 0.24g of benzoyl peroxide were added to 60mL of an aqueous solution containing 0.1g of sodium dodecyl sulfate, and the mixture was phacoemulsified; adding the emulsion into the reaction liquid after swelling for 12 hours, and continuing swelling for 6 hours; finally, carrying out polymerization reaction for 16h at 70 ℃ under the protection of nitrogen atmosphere to obtain porous polymer microspheres; hydrolyzing 1g of porous polymer microspheres with 30mL of 5wt% sodium hydroxide aqueous solution at 80 ℃ for 3 hours, washing with distilled water to be neutral after the hydrolysis is finished, and condensing and refluxing with 30mL of 0.2mol/L sulfuric acid aqueous solution at 80 ℃ for 4 hours to obtain functionalized porous polymer microspheres;
(2) Dispersing 1g of functionalized porous polymer microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing the mixture by ultrasonic, and transferring the mixture into a three-neck flask to be slowly stirred for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 8h; and after the product is cooled, magnetically separating, and cleaning the product for 3 to 4 times by pure water to obtain the porous magnetic polymer microsphere.
As is clear from a comparison of example 1 and example 4, the size of the magnetic nanoclusters prepared in example 1 is 100.+ -. 10nm and the size of the magnetic nanoclusters prepared in example 4 is 45.+ -. 10nm.
Example 5
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Synthesis of functionalized porous polymer microspheres: firstly, adding 30mL of isopropanol and 20mL of distilled water into a 100mL three-neck flask, then adding 0.75g of polyvinylpyrrolidone, 5mL of styrene and 0.10g of azodiisobutyronitrile into the three-neck flask, and heating to 75 ℃ under the protection of nitrogen to react for 12 hours to obtain polystyrene seed microspheres with the particle size of about 1 mu m; 1.2mL of toluene and 3.6mL of dibutyl phthalate are added into 60mL of aqueous solution containing 0.1g of sodium dodecyl sulfate, ultrasonic emulsification is completed, and then 0.2 g of polystyrene seed microsphere is added into the mixture to swell for 12 hours at room temperature; 5mL of methyl methacrylate, 1mL of divinylbenzene, 1mL of glycidyl methacrylate and 0.24g of benzoyl peroxide were added to 60mL of an aqueous solution containing 0.1g of sodium dodecyl sulfate, and the mixture was phacoemulsified; adding the emulsion into the reaction liquid after swelling for 12 hours, and continuing swelling for 6 hours; finally, carrying out polymerization reaction for 16h at 70 ℃ under the protection of nitrogen atmosphere to obtain porous polymer microspheres; hydrolyzing 1g of porous polymer microspheres with 30mL of 5wt% sodium hydroxide aqueous solution at 80 ℃ for 3 hours, washing with distilled water to be neutral after the hydrolysis is finished, and condensing and refluxing with 30mL of 0.2mol/L sulfuric acid aqueous solution at 80 ℃ for 4 hours to obtain functionalized porous polymer microspheres;
(2) Dispersing 1g of functionalized porous polymer microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing the mixture by ultrasonic, and transferring the mixture into a three-neck flask to be slowly stirred for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 10h; after the product is cooled, magnetically separating, washing with tannic acid for 3-4 times, and then washing with distilled water to neutrality to obtain the porous magnetic polymer microsphere with better dispersivity. When the magnetic polymer microspheres are washed, tannic acid is adopted to wash, so that the dispersibility of the magnetic microspheres in water is improved, the subsequent surface modification is facilitated, and the magnetic property of the microspheres is not influenced.
After washing with tannic acid, the surface of the magnetic polymer microsphere is modified by tannic acid, and the tannic acid has a large number of phenolic hydroxyl groups, has a large molecular structure and large steric hindrance, so that the magnetic polymer microsphere modified by tannic acid has better suspension property in water.
Example 6
(1) Synthesis of carboxylated polystyrene microspheres: 50mL of distilled water is added into a 100mL three-neck flask, then 5mL of styrene, 0.4mL of acrylic acid, 0.5mL of divinylbenzene and 0.05g of potassium persulfate are added into the three-neck flask under magnetic stirring, the temperature is raised to 75 ℃ under the protection of nitrogen for reaction for 20 hours, and the carboxylated polystyrene microspheres with the particle size of about 0.8 mu m are obtained after centrifugal washing;
(2) Dispersing 1g of carboxylated polystyrene microspheres in 80mL of ethylene glycol, adding 6g of ferric trichloride hexahydrate, 6g of sodium acetate and 3.5g of polyethylene glycol (molecular weight of polyethylene glycol-8000) into the mixture, uniformly dispersing by ultrasonic, and transferring the mixture into a three-neck flask to be slowly stirred for 24 hours at 60 ℃;
(3) Transferring the reaction solution into a 100mL high-pressure reaction kettle, and heating to 200 ℃ for reaction for 10h; and after the product is cooled, magnetically separating, washing with tannic acid for 3-4 times, and then washing with distilled water until the product is neutral to obtain the magnetic polymer microsphere.
Example 6 magnetic polymer microspheres are prepared by synthesizing magnetic nanoclusters from non-porous carboxylated polystyrene microspheres through a solvothermal method, and the magnetism of the products of comparative example 1 and example 6 can be obviously found that the magnetic nanoclusters of example 6 are both on the surface of the microspheres, so that the surface energy is larger, the later functional encapsulation is not favored, while the porous polymer microspheres are used as a master nucleus for preparing the magnetic polymer microspheres in example 1, on one hand, the synthesized magnetic nanoclusters can enable the magnetic nanoclusters to grow in the pore diameter mostly by controlling the particle size of the magnetic nanoclusters, and on the other hand, the porous polymer microspheres can provide higher specific surface area, stability and rich functional groups, so that the higher magnetic content of the polymer microspheres is realized.
Example 7
The preparation method of the porous magnetic polymer microsphere comprises the following steps:
(1) Synthesis of functionalized porous polymer microspheres: firstly, adding 30mL of isopropanol and 20mL of distilled water into a 100mL three-neck flask, then adding 0.75g of polyvinylpyrrolidone, 5mL of styrene and 0.10g of azodiisobutyronitrile into the three-neck flask, and heating to 75 ℃ under the protection of nitrogen to react for 12 hours to obtain polystyrene seed microspheres with the particle size of about 1 mu m; 1.2mL of toluene and 3.6mL of dibutyl phthalate are added into 60mL of aqueous solution containing 0.1g of sodium dodecyl sulfate, ultrasonic emulsification is completed, and then 0.2 g of polystyrene seed microsphere is added into the mixture to swell for 12 hours at room temperature; 5mL of methyl methacrylate, 1mL of divinylbenzene, 1mL of glycidyl methacrylate and 0.24g of benzoyl peroxide were added to 60mL of an aqueous solution containing 0.1g of sodium dodecyl sulfate, and the mixture was phacoemulsified; adding the emulsion into the reaction liquid after swelling for 12 hours, and continuing swelling for 6 hours; finally, carrying out polymerization reaction for 16h at 70 ℃ under the protection of nitrogen atmosphere to obtain porous polymer microspheres; hydrolyzing 1g of porous polymer microspheres with 30mL of 5wt% sodium hydroxide aqueous solution at 80 ℃ for 3 hours, washing with distilled water to be neutral after the hydrolysis is finished, and condensing and refluxing with 30mL of 0.2mol/L sulfuric acid aqueous solution at 80 ℃ for 4 hours to obtain functionalized porous polymer microspheres;
(2) Synthesis of porous magnetic polymer microspheres: dispersing 1g of functionalized porous polymer microspheres in 50mL of distilled water, adding 5.5g of ferrous chloride tetrahydrate and 9g of ferric chloride hexahydrate into the mixture, carrying out ultrasonic homogenization, transferring the mixture into a 100mL three-neck flask, carrying out mechanical stirring at 1000rpm to enable the mixture to be rapidly and uniformly dispersed, then raising the temperature to 70 ℃ and continuously stirring for 1h, rapidly adding 8mL of ammonia water into the system, carrying out reaction for 0.5h, carrying out magnetic absorption separation after the product is cooled, washing 3-4 times by using tannic acid, and then washing to be neutral by using distilled water to obtain the porous magnetic polymer microspheres.
In the embodiment 7, the magnetic nanoclusters are not synthesized by a solvothermal method, but the ferroferric oxide nanoparticles are prepared by a conventional coprecipitation method, and the transmission electron microscope shows that the free ferroferric oxide nanoparticles synthesized by the coprecipitation method are more, are unfavorable for later encapsulation, and have much weaker magnetic responsivity than the magnetic nanoclusters synthesized by the solvothermal method compared with the magnetic nanoclusters in the embodiment 1.
Table 1 shows the magnetic content, dispersibility, and magnetic nanocluster particle size of the products of examples 1 to 7

Claims (10)

1. The preparation method of the porous magnetic polymer microsphere is characterized by comprising the following steps:
(1) The polystyrene seed microsphere is swelled in the first step under the action of a swelling agent and a surfactant, swelled in the second step under the action of a functional monomer, an initiator and the surfactant, and the functionalized porous polymer microsphere is prepared;
(2) Mixing porous polymer microspheres, an iron source, an alkali source, polyalcohol and a surfactant, fully absorbing under stirring, and capturing the iron source in a reaction system by functional groups on the surfaces of the polymer microspheres to perform chelation reaction;
(3) And (3) transferring the mixture material fully absorbed in the step (2) into a high-pressure reaction kettle, and preparing the magnetic polymer microsphere through a solvothermal method.
2. The preparation method of the porous magnetic polymer microsphere is characterized by comprising the following steps:
(1) Adding a reaction monomer and an initiator into a solvent to perform precipitation polymerization reaction, and obtaining a spherical polymer after the reaction is finished; adding a cross-linking agent or adding the cross-linking agent and a reaction monomer into a reaction system, and carrying out polymerization again to obtain microspheres with core-shell structures after the reaction is finished, wherein the microspheres consist of spherical polymers and cross-linked shell layers coated outside the spherical polymers; centrifugally washing the microsphere with the non-crosslinked core and the crosslinked shell, and removing spherical polymers in the crosslinked shell to obtain the hydrogel hollow microsphere with a cavity structure;
(2) Mixing hydrogel hollow microspheres, an iron source, an alkali source, polyalcohol and a surfactant, fully absorbing under stirring, and capturing the iron source in a reaction system by functional groups on the surfaces of the microspheres to perform chelation reaction;
(3) And (3) transferring the mixture material fully absorbed in the step (2) into a high-pressure reaction kettle, and preparing the magnetic polymer microsphere through a solvothermal method.
3. The method for preparing the porous magnetic polymer microsphere according to claim 1, wherein: in the step (1), the functional monomer is a monomer with at least two functional groups of amino, carboxyl, epoxy or hydroxyl; the functional groups on the surface of the functionalized porous polymer microsphere are at least two of amino, carboxyl, epoxy or hydroxyl, and the crosslinking degree is 5-25%.
4. The method for preparing the porous magnetic polymer microsphere according to claim 2, wherein: in the step (1), the solvent is acetonitrile or a mixed solvent of acetonitrile and ethanol; the initiator is azodiisobutyronitrile, azodiisovaleronitrile or benzoyl peroxide; the reaction monomer is one or more of acrylic acid, methacrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxyethyl, hydroxypropyl methacrylate, acrylamide, methacrylamide or N-isopropyl acrylamide; the cross-linking agent is divinylbenzene, methylene bisacrylamide and dimethyl glycol ester and other cross-linking agents containing more than two unsaturated ethylenic bonds.
5. The method for preparing the porous magnetic polymer microsphere according to claim 1 or 2, wherein: in the step (2), the absorption temperature is 20-80 ℃ and the absorption time is 0.5-24 h.
6. The method for preparing the porous magnetic polymer microsphere according to claim 1 or 2, wherein: in the step (2), the mass-to-volume ratio of the porous polymer microsphere or the hydrogel hollow microsphere, the iron source, the alkali source, the polyol and the surfactant is 1g: 6-10 g: 6-10 g: 3.5-5 g: 80-100 mL.
7. The method for preparing the porous magnetic polymer microsphere according to claim 6, wherein: the iron source is one or a combination of a plurality of ferric trichloride hexahydrate, ferric trichloride, ferrous chloride tetrahydrate or ferrous sulfate heptahydrate; the polyol is one of ethylene glycol, 1, 2-propylene glycol or glycerol; the alkali source is one of sodium acetate, sodium citrate, ammonium acetate, triethylamine, ammonia water or sodium hydroxide; the surfactant is one of polyacrylic acid, sodium polyacrylate, polyacrylamide or polyethylene glycol.
8. The method for preparing the porous magnetic polymer microsphere according to claim 1, wherein: in the step (3), magnetic Fe is synthesized in situ on the pores and the surface of the porous polymer microsphere by a solvothermal method 3 O 4 The reaction temperature of the nanoclusters is 150-220 ℃, the temperature rising rate is 50-200 ℃/h, and the reaction time is 6-36 h.
9. The method for preparing the porous magnetic polymer microsphere according to claim 1, wherein: in the step (3), magnetic Fe is synthesized in situ in the hollow microsphere cavity and on the surface of the hydrogel by a solvothermal method 3 O 4 The reaction temperature of the nanoclusters is 150-220 ℃, the temperature rising rate is 50-200 ℃/h, and the reaction time is 6-36 h.
10. The method for preparing the porous magnetic polymer microsphere according to claim 8 or 9, wherein: in the step (3), the diameter of the magnetic polymer microsphere is 0.8-5 mu m, and the magnetic Fe 3 O 4 The diameter of the nanoclusters is 50-500 nm.
CN202310446440.9A 2023-04-24 2023-04-24 Preparation method of porous magnetic polymer microsphere Pending CN116444730A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310446440.9A CN116444730A (en) 2023-04-24 2023-04-24 Preparation method of porous magnetic polymer microsphere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310446440.9A CN116444730A (en) 2023-04-24 2023-04-24 Preparation method of porous magnetic polymer microsphere

Publications (1)

Publication Number Publication Date
CN116444730A true CN116444730A (en) 2023-07-18

Family

ID=87133564

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310446440.9A Pending CN116444730A (en) 2023-04-24 2023-04-24 Preparation method of porous magnetic polymer microsphere

Country Status (1)

Country Link
CN (1) CN116444730A (en)

Similar Documents

Publication Publication Date Title
CN103554325B (en) A kind of preparation method of functional hollow polymer microballoon
Ma et al. Hydrophilic dual‐responsive magnetite/PMAA core/shell microspheres with high magnetic susceptibility and ph sensitivity via distillation‐precipitation polymerization
CN112666140B (en) Poly (undecylenic acid-divinylbenzene) -coated magnetic fluorescently encoded microspheres
CN109322155B (en) Preparation method of triple-responsiveness nanofiber hydrogel
CN104559327B (en) A kind of surface modified nano calcium carbonate with core shell structure and preparation method thereof
CN1923857A (en) Preparation method of high magnetism content monodisperse hydrophilicity magnetic composite microsphere
CN109985584B (en) Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres
CN112592423B (en) Monodisperse magnetic microspheres
Ma et al. Preparation and surface modification of non-porous micron-sized magnetic poly (methyl acrylate) microspheres
CN112175150A (en) Novel preparation method of functionalized porous magnetic microspheres
CN114093586A (en) Polymer-coated magnetic microsphere and preparation method thereof
CN115304882B (en) Preparation method of polymer coated porous magnetic polymer microsphere with controllable topological structure on surface
Huang et al. Synthesis of monodisperse hollow polymer microspheres with functional groups by distillation precipitation polymerization
CN114192079B (en) Magnetic hollow polymer microsphere and preparation method and application thereof
CN116444730A (en) Preparation method of porous magnetic polymer microsphere
CN1772366A (en) Hollow microcapsule preparing process
CN114106254B (en) Method for preparing functionalized magnetic polymer microsphere by miniemulsion polymerization method using porous microsphere as template
CN105801778B (en) Synthetic method of single-layer imprinted polymer based on surface of silicon dioxide microsphere
Du et al. Surface modification of silica nanoparticles by grafting poly (methyl methacrylate) using atom transfer radical polymerisation with activators regenerated by electron transfer
Man et al. Fabrication of Fe 3 O 4@ poly (methyl methacrylate-co-glycidyl methacrylate) microspheres via miniemulsion polymerization using porous microspheres as templates for removal of cationic dyes
CN112694570B (en) Ambient temperature sensor based on nano particles
JP2023524994A (en) Monodisperse superparamagnetic particles and method for producing the same
CN110935405B (en) Preparation method of magnetic polystyrene microspheres with surfaces rich in double bonds
CN115710373B (en) Preparation method of hydrogel magnetic microsphere
Lu et al. Synthesis and characterization of magnetic polymer microspheres with a core–shell structure

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