CN113578214B - Micron-sized porous magnetic microsphere and preparation method and application thereof - Google Patents
Micron-sized porous magnetic microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of micron-sized porous magnetic microspheres, which comprises the following steps: step one, preparing seed microspheres by a dispersion method; step two, depositing magnetic particles; step three, magnetic particles are subjected to surface SiO 2 Coating; step four, carrying out seed swelling copolymerization to obtain swelling microspheres; and step four, repeating the steps of depositing the magnetic particles in the step two to swelling and copolymerizing the seeds in the step four according to the sequence to obtain the micron-sized porous magnetic microspheres. The beneficial effects of the invention are as follows: the invention adopts a method combining a multi-step swelling copolymerization method and a chemical precipitation method to obtain the micron-sized porous magnetic microsphere, and the porous magnetic material has excellent characteristics of high strength, high specific surface, acid and alkali resistance and the like, so that the porous magnetic microsphere can be widely applied to the field of biological micromolecules and can bring larger dominant polymerization when combined with an automatic instrument.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a micron-sized porous magnetic microsphere, a preparation method and application thereof.
Background
Biological sample pretreatment refers to a method of separating a target compound from a biological medium (e.g., plasma, tissue, urine, etc.) by physicochemical means. With the continuous development of pharmaceutical disciplines, new active compounds are emerging, and the number of drugs to be subjected to pharmacokinetic evaluation is increasing, which is more urgent for in vivo drug analysis techniques to enable high throughput analysis and rapid pretreatment in a short time.
The traditional pretreatment method mainly adopts a combination mode of a solid phase extraction technology and a 96-well plate, and the flux is increased to 96 positions, but the traditional pretreatment method has the defects of complicated manual operation steps, long time, low yield and large error, and is difficult to automatically operate in experiments. The magnetic separation technology can adsorb and release the magnetic microspheres through the increase or the disappearance of the magnetic field, thereby realizing the separation and the purification of the biological sample.
At present, the outer surface of the biological nanometer magnetic bead is provided with carboxyl and amino, and the application in the field of macromolecular detection is more and more extensive, but the problem that the outer surface of the biological nanometer magnetic bead is too small can hardly be applied to the pretreatment of biological small molecules.
The invention adopts a method combining a multi-step swelling copolymerization method and a chemical precipitation method to obtain the micron-sized porous magnetic material, and the porous magnetic material has the excellent characteristics of high strength, high specific surface, acid and alkali resistance and the like, so that the porous magnetic material can be widely applied to the field of biological micromolecules and can bring greater advantages when being combined with an automatic instrument.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a micron-sized porous magnetic microsphere and a preparation method thereof.
The aim of the invention is achieved by the following technical scheme.
A preparation method of micron-sized porous magnetic microspheres comprises the following steps:
step one, preparing seed microspheres by a dispersion method;
step two, depositing magnetic particles on the surfaces of the seed microspheres in the step one to form magnetic composite microspheres;
step three, carrying out surface SiO on the magnetic composite microsphere obtained in the step two 2 Coating to obtain SiO attached to the surface 2 Is a composite microsphere of (a);
step four, carrying out seed swelling copolymerization on the magnetic composite microspheres in the step three to obtain swelled microspheres;
and fifthly, repeating the step of swelling and copolymerizing the seeds deposited in the step two to the step four according to the sequence to obtain the micron-sized porous magnetic microsphere.
Preferably, the specific method for preparing the polymer microsphere by the dispersion method in the first step is as follows: dissolving the dispersing agent in alcohol, deoxidizing with nitrogen, stirring, heating, adding monomer containing ethylene double bond dissolved with initiator, reacting for more than 6 hours, and cooling to room temperature after the reaction.
In any of the above embodiments, it is preferable that the seed microsphere in the first step has a particle diameter of 1nm to 5um.
From any of the above, it is preferable that SiO in the third step 2 The specific method for surface coating comprises the following steps: adding polymer microsphere after swelling of single seed into dispersion liquid, adding concentrated ammonia water or 5-20M concentrated sodium hydroxide alkali solution, and washing to obtain SiO attached to surface 2 Is a composite microsphere of (a).
It is preferable from any of the above schemes that the specific method for the seed swelling copolymerization in the fourth step is:
the first step, suspending the magnetic composite microsphere prepared in the third step in an aqueous solution containing a stabilizer;
step two, fully mixing ethylene monomers, comonomers, an initiator and a pore-forming agent, adding the mixture into an aqueous solution dissolved with a stabilizer and a surfactant, and homogenizing and stirring at a high speed to prepare a nano emulsion;
and thirdly, slowly dripping the emulsion prepared in the second step into the aqueous solution prepared in the first step by using a dropping funnel, dripping and swelling, heating and polymerizing, and finishing one-step swelling copolymerization.
In any of the above embodiments, it is preferable that the vinyl monomer and the comonomer in the second step are each any one of styrene, divinylbenzene, methyl methacrylate, acrylic acid, acrylic matrix, acrylamide, and N-vinylpyrrolidone.
In any of the above embodiments, preferably, the initiator in the second step is any one of benzoyl peroxide, tert-butyl peroxybenzoate, and azobisisobutyronitrile.
In any of the above embodiments, preferably, the porogen in the second step is any one of toluene, n-heptane, and liquid paraffin.
In any of the above embodiments, it is preferable that the polymer electrolyte in the second step is any one of cetyltrimethylammonium bromide, polydidecyldimethylammonium chloride, polytrimethylallyl ammonium chloride, and polydidecyldimethylammonium chloride.
It is preferred from any of the above aspects that the stabilizer in the second step is any one of a water-soluble cellulose ether, polyvinylpyrrolidone or hydroxypropyl cellulose steric stabilizer.
It is preferable from any of the above schemes that the weight percentages of the ethylene monomer, the comonomer, the initiator, and the porogen in the second step are: 20-60:10-60:0.2-1.5:100-600.
It is preferable in any of the above embodiments that the weight percentages of the vinyl monomer, the stabilizer, the surfactant, and the water in the second step are: 20-80:0.05-0.5:0.5-5:50-500.
In any of the above modes, preferably, in the third step, the high-speed homogenizer is used for stirring, the stirring time is 0.2-10min, and the particle size of the emulsion is 1-200nm.
In any of the above embodiments, the obtained microporous magnetic microspheres preferably have a particle size of 0.2um to 150um and a specific surface area of 10 to 800m 2 And/g, the average pore diameter is 0.5-15nm.
The micron-sized porous magnetic microsphere prepared by the preparation method of the micron-sized porous magnetic microsphere is characterized in that: the composite magnetic material comprises seed microspheres, wherein the outer surfaces of the seed microspheres are swelled to copolymerize the multi-layer magnetic particles, and the outer layers of the silicon dioxide are swelled to copolymerize the organic comonomer.
Preferably, the particle size of the microsphere is 0.2um-150um, and the specific surface area is 10-800m 2 And/g, the average pore diameter is 0.5-15nm. Preferably 2um-150um, specific surface area 200-800m 2 And/g, the average pore diameter is 0.5-15nm.
The micron-sized porous magnetic microsphere is applied to the preparation of high polymer magnetic microsphere.
The beneficial effects of the invention are as follows:
the invention provides a method for combining a multi-step swelling copolymerization method and a chemical precipitation method to obtain a micron-sized porous magnetic material, which has the excellent characteristics of high strength, high specific surface, acid and alkali resistance and the like, so that the porous magnetic material can be widely applied to the field of biological micromolecules and can bring greater advantages when combined with an automatic instrument.
Detailed Description
The technical scheme of the invention is further described by specific examples.
1. Preparation method
A preparation method of micron-sized porous magnetic microspheres comprises the following steps:
step one, preparing seed microspheres by a dispersion method; the specific method for preparing the polymer microsphere by the dispersion method in the first step comprises the following steps: dissolving the dispersing agent in alcohol, deoxidizing with nitrogen, stirring, heating, adding monomer containing ethylene double bond dissolved with initiator, reacting for more than 6 hours, and cooling to room temperature after the reaction. The seed microsphere in the first step has a particle size of 200nm-5um, preferably 1-2um. The polymerization system of the dispersion polymerization mode is ethanol, acetonitrile, water, toluene and methanol; specifically, the vinyl double bond monomer used in the first step of the microsphere is one or two of styrene, divinylbenzene, vinyl acetate and acrylic ester, and is synthesized by emulsion polymerization.
Step two, ferric oxide is deposited on the surfaces of the seed microspheres in the step one, so as to form magnetic composite microspheres; step two, a layer of ferroferric oxide is deposited on the surface of the seed microsphere through FeCl 3 ·6H 2 O and FeCl 2 ·4H 2 O is synthesized by coprecipitation method, fe 3 O 4 The particle size of the nano particles is 10-100nm; fe (Fe) 2+ /Fe 3+ The ratio is in the range of 0.5-3, and the reaction temperature is 50-90 ℃.
Step three, hydrolyzing the magnetic composite microsphere obtained in the step two in an alkaline environment to carry out SiO on the surface 2 Surface coating, using hexadecyl trimethyl ammonium bromide as surfactant and structure directing agent, dispersing the magnetic spherical microsphere in the above step in microemulsion (ethanol/water), forming oil drop by Tetraethoxysilane (TEOS), hydrolyzing and polymerizing TEOS by ammonia water to synthesize surface-attached SiO 2 Is a composite microsphere of (a);
SiO in the third step 2 The specific method for surface coating comprises the following steps: adding polymer microsphere after swelling of single seed into dispersion liquid, adding concentrated ammonia water or 5-20M concentrated sodium hydroxide alkali solution, and washing to obtain SiO attached to surface 2 Is a composite microsphere of (a).
Step four, coating SiO in the step three 2 The magnetic composite microsphere is subjected to seed swelling copolymerization to obtain a swelling microsphere;
step five, repeating the step of swelling and copolymerizing the seeds deposited in the step two to the step four in sequence, after circulating to the step four, adopting the steps of conventional method, such as filtration, extraction, cleaning, magnetic attraction and the like, and measuring the particle size, the particle size distribution and the specific surface area of the obtained product to obtain the micron-sized porous magnetic microsphere,
the specific method for swelling and copolymerizing the seeds in the fourth step comprises the following steps:
the first step, suspending the magnetic composite microsphere prepared in the third step in an aqueous solution containing a stabilizer;
step two, fully mixing ethylene monomers, comonomers, an initiator and a pore-forming agent, adding the mixture into an aqueous solution in which a stabilizer and a surfactant are dissolved, and stirring the mixture by a high-speed homogenizer to prepare nano emulsion, wherein the stirring time is 3-10min, and the particle size of the emulsion is 10-200nm; the stabilizer is any one of water-soluble cellulose ether, polyvinylpyrrolidone or hydroxypropyl cellulose steric stabilizer; the weight percentages of the ethylene monomer, the comonomer, the initiator and the porogen are as follows: 20-60:10-60:0.2-1.5:100-600; the weight percentages of the ethylene monomer, the stabilizer, the surfactant and the water are as follows: 20-80:0.05-0.5:0.5-5:50-500.
Wherein the ethylene monomer and the comonomer are any one of styrene, divinylbenzene, methyl methacrylate, acrylic acid matrix, acrylamide and N-vinyl pyrrolidone respectively.
The initiator is any one of benzoyl peroxide, tert-butyl peroxybenzoate and azobisisobutyronitrile.
The pore-forming agent is any one of toluene, n-heptane and liquid paraffin.
The polymer electrolyte is any one of cetyltrimethylammonium bromide, polydidecyl dimethyl ammonium chloride, polytrimethylallyl ammonium chloride, and polydidecyl dimethyl ammonium chloride.
And thirdly, slowly dripping the emulsion prepared in the second step into the aqueous solution prepared in the first step by using a dropping funnel, dripping and swelling, heating and polymerizing, and finishing one-step swelling copolymerization.
The particle size of the micron-sized porous magnetic microsphere obtained by the preparation method of the micron-sized porous magnetic microsphere is 0.2um-150um, and the specific surface area is 10-800m 2 And/g, the average pore diameter is 0.5-15nm.
2. The micron-sized porous magnetic microsphere prepared by the method
The micron-sized porous magnetic microsphere prepared by the preparation method of the micron-sized porous magnetic microsphere is characterized in that: the magnetic particle comprises seed microspheres, wherein the outer surfaces of the seed microspheres are swelled to copolymerize multi-layer magnetic particles, the outermost layers of the magnetic particles are coated with silicon dioxide, and the outer layers of the silicon dioxide are swelled to copolymerize organic comonomers.
Preferably, the particle size of the microsphere is 0.2um-150um, and the specific surface area is 10-800m 2 And/g, the average pore diameter is 0.5-15nm.
3. Application of micron-sized porous magnetic microsphere
The micron-sized porous magnetic microsphere is applied to the preparation of high polymer magnetic microsphere.
Specifically, after SiO2 is coated on the micron-sized porous magnetic microsphere, final swelling polymerization is further carried out according to the required groups, phenyl can be directly swelled and copolymerized again by divinylbenzene and styrene, carboxyl can be swelled and copolymerized again by adding acrylic acid and methyl acrylate into a comonomer, and pyrrolidone groups can be copolymerized again by adding N-vinyl pyrrolidone into the comonomer.
Example 1
1. Preparation of seed microspheres
3.0g of dispersing agent PVP, 70g of ethanol and 30g of water are added into a 250ml four-port glass reaction bottle, stirred and pre-dispersed for 30min in an oil bath at 68 ℃, and nitrogen is introduced to replace air in a reactor; then, 0.5g of AIBN and 10g of monomer styrene were prepared into a solution and injected into a reactor to react at 70℃for 24 hours. After the reaction, cooling to room temperature for standby, wherein the obtained seed microsphere is 1um.
2、Fe 3 O 4 Deposited on the surface of the microsphere
100ml of the seed microsphere is taken, a 2 liter four-mouth flask is added, 1000ml of deionized water is added into the four-mouth reaction flask, and stirring is carried out for 30min. 6.1g FeCl3.6H2O and 3.8g FeCl2.4H2O were weighed and dissolved in the stirring solution. Introducing high-purity nitrogen for 30min to remove oxygen in the reaction system, dropwise adding 20ml of 28% concentrated ammonia water, and reacting at 70 ℃ for 30min. After the reaction is finished, cooling to room temperature, separating the magnet, washing with ultrapure water to be neutral, washing with methanol for 3 times, and drying in vacuum at 50 ℃.
3. Seed swelling copolymerization 1
20g of the magnetic microsphere obtained in the previous step is taken and added into a 1000ml four-necked flask, then 0.6g of hydroxypropyl methylcellulose and 500ml of water are added, and the mixture is stirred and heated to 40 ℃ and dispersed for 3 hours by ultrasonic stirring at 40 ℃.
10g of divinylbenzene, 20g of styrene, 40g of toluene and 0.6g of azobisisobutyronitrile were mixed, added into 200ml of water containing 0.1g of hydroxypropyl methylcellulose and 1g of Triton X-405, stirred and stirred at high speed for 3 minutes to obtain an emulsion, slowly dropped into the above solution at 40 ℃ for 1 hour, and swelling was continued for another 4 hours after the dropping was completed. The polymerization was continued for 12 hours with continued heating to 88 ℃. Filtering and washing by conventional method. The particle diameter of the obtained copolymer microsphere is concentrated between 2 and 2.5um, the distribution is narrow, and the specific surface area is 285m 2 /g。
4. Secondary deposition of ferroferric oxide on the surface of the swelling microsphere
Taking 20g of microspheres after seed swelling, adding the microspheres into a 1 liter four-mouth flask, adding 500ml of deionized water into the four-mouth reaction flask, and stirring for 30min. Weigh 3.1g FeCl 3 ·6H 2 O and 1.9g FeCl 2 ·4H 2 O is added into the stirring solution to be dissolved. Introducing high-purity nitrogen for 30min to remove oxygen in the reaction system10ml of 28% concentrated ammonia water was added dropwise thereto and reacted at 70℃for 30 minutes. After the reaction is finished, cooling to room temperature, separating the magnet, washing with ultrapure water to be neutral, washing with methanol for 3 times, and drying in vacuum at 50 ℃.
5、SiO 2 Surface coating
Taking 20g of microspheres after secondary deposition, adding the microspheres into a 2000ml four-mouth bottle, adding 700ml of absolute ethyl alcohol and 300ml of deionized water, and performing ultrasonic dispersion for 30min. 2.4g of cetyltrimethylammonium bromide is added, the mixture is stirred and reacted for 1h at 40 ℃, 2ml of ammonia water is added, the mixture is stirred for 10min, 5g of TEOS and 30ml of ethanol are gradually added dropwise, and after the dropwise addition is completed, the reaction is carried out for 24h at 40 ℃. And magnetically separating the materials after discharging, washing with methanol for three times, and drying at 50 ℃.
6. Seed swelling copolymerization 2-carboxyl porous magnetic bead microsphere
20g of the magnetic microsphere obtained in the previous step is taken and added into a 1000ml four-necked flask, then 0.6g of hydroxypropyl methylcellulose and 500ml of water are added, and the mixture is stirred and heated to 40 ℃ and dispersed for 3 hours by ultrasonic stirring at 40 ℃.
10g of divinylbenzene, 20g of methyl acrylate, 40g of toluene and 0.6g of azobisisobutyronitrile were mixed, added to 200ml of water containing 0.1g of hydroxypropyl methylcellulose and 1g of Triton X-405, and stirred homogeneously at a high speed for 3 minutes to obtain an emulsion, which was slowly added dropwise to the above solution at 40℃for a total of 1 hour, and swelling was continued for another 4 hours after completion of the dropwise addition. The polymerization was continued for 12 hours with heating to 82 ℃. Filtering and washing by conventional method.
The swollen microspheres were hydrolyzed by adding 500ml of 1mol NaOH for 4 hours. Is a carboxyl porous magnetic bead microsphere.
The particle diameter of the obtained copolymer microsphere is concentrated between 8 and 9um, and the specific surface area is 525m 2 /g。
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (12)
1. A preparation method of micron-sized porous magnetic microspheres is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing seed microspheres by a dispersion method;
step two, depositing ferroferric oxide on the surface of the seed microsphere in the step one to form a magnetic composite microsphere, wherein a layer of ferroferric oxide is deposited on the surface of the seed microsphere through FeCl 3 ·6H 2 O and FeCl 2 ·4H 2 O coprecipitation method for synthesizing Fe 3 O 4 The particle size of the nano particles is 10-100nm; fe (Fe) 2+ /Fe 3+ The ratio is 0.5-3, and the reaction temperature is 50-90 ℃;
step three, carrying out surface SiO on the magnetic composite microsphere obtained in the step two 2 Coating to obtain SiO attached to the surface 2 Is a composite microsphere of (a);
step four, adhering SiO to the surface in the step three 2 Carrying out seed swelling copolymerization on the composite microspheres to obtain swelling microspheres;
step five, repeating the step of swelling and copolymerizing the seeds deposited in the step two to the step four according to the sequence to obtain the micron-sized porous magnetic microspheres;
the specific method for swelling and copolymerizing the seeds in the fourth step comprises the following steps:
the first step, adhering SiO to the surface prepared in the third step 2 Suspending the composite microspheres of (2) in an aqueous solution comprising a stabilizer;
step two, fully mixing ethylene monomers, comonomers, an initiator and a pore-forming agent, adding the mixture into an aqueous solution dissolved with a stabilizer and a surfactant, and homogenizing and stirring at a high speed to prepare a nano emulsion;
and thirdly, slowly dripping the emulsion prepared in the second step into the aqueous solution prepared in the first step by using a dropping funnel, dripping and swelling, heating and polymerizing, and finishing one-step swelling copolymerization.
2. The method for preparing the micron-sized porous magnetic microsphere according to claim 1, wherein the method comprises the following steps: the particle size of the seed microsphere in the first step is 1nm-5um.
3. The method for preparing the micron-sized porous magnetic microsphere according to claim 1, wherein the method comprises the following steps: the weight percentages of the ethylene monomer, the comonomer, the initiator and the pore-forming agent in the second step are as follows: 20-60:10-60:0.2-1.5:100-600.
4. The method for preparing the micron-sized porous magnetic microsphere according to claim 1, wherein the method comprises the following steps: the weight percentages of the ethylene monomer, the stabilizer, the surfactant and the water in the second step are as follows: 20-80:0.05-0.5:0.5-5:50-500.
5. The method for preparing the micron-sized porous magnetic microsphere according to claim 1, wherein the method comprises the following steps: and in the second step, the high-speed homogenizing stirring is carried out for 0.2-10min, and the particle size of the emulsion is 1-200nm.
6. The method of claim 1, wherein the vinyl monomer and the comonomer in the second step are each any one of styrene, divinylbenzene, methyl methacrylate, acrylic acid, an acrylic matrix, acrylamide, and N-vinylpyrrolidone.
7. The method for preparing a microporous magnetic microsphere according to claim 1, wherein the initiator in the second step is any one of benzoyl peroxide, tert-butyl peroxybenzoate and azobisisobutyronitrile.
8. The method of claim 1, wherein the porogenic agent in the second step is any one of toluene, n-heptane, and liquid paraffin.
9. The method of claim 1, wherein the stabilizer used in the second step is any one of water-soluble cellulose ether, polyvinylpyrrolidone and hydroxypropyl cellulose steric stabilizer.
10. A micron-sized porous magnetic microsphere prepared by the preparation method of the micron-sized porous magnetic microsphere according to any one of claims 1 to 9, which is characterized by comprising seed microspheres, outer surface swelling copolymerized multi-layer magnetic particles of the seed microspheres, and outer layer swelling copolymerized organic comonomers of silicon dioxide.
11. The microporous magnetic microsphere of claim 10, wherein the particle size of the microporous magnetic microsphere is 0.2um to 150um and the specific surface area is 10m to 800m 2 And/g, the average pore diameter is 0.5-15nm.
12. The method of claim 10, wherein the microporous magnetic microsphere is used for preparing a high polymer magnetic microsphere.
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