CN115584004A - Method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres - Google Patents
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Abstract
The invention discloses a method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres, which comprises the following steps: dissolving a dispersing agent in a mixed medium of alcohol and water under nitrogen to form a homogeneous solution; adding an initiator and styrene into the homogeneous solution, and uniformly dispersing to obtain a mixed system; and (3) dropwise adding a cross-linking agent alcohol solution into the mixed system at the temperature of 60-80 ℃, and reacting for 8-48 h at the temperature of 60-80 ℃ after dropwise adding to obtain the micron-sized monodisperse cross-linked polystyrene microspheres. The invention can prepare the crosslinked polystyrene microspheres with monodispersity, good sphericity and particle size of 1.20-3.68 mu m, and can be widely applied to the fields of spacers, biomedicine, standard measurement, chemical synthesis, microelectronics and the like.
Description
Technical Field
The invention relates to the field of polymer microsphere materials, in particular to a method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres.
Background
The crosslinked polystyrene microsphere has good physical and chemical stability, higher mechanical strength and specific surface area and regular spherical morphology, and is widely applied to the fields of spacers, chromatographic column packing, standard metering, immunoassay, optoelectronic devices and the like.
The traditional method for preparing the crosslinked polystyrene microspheres mainly comprises a dispersion polymerization method and a seed swelling method. The dispersion polymerization is a preparation method in which a dispersant, an initiator, a crosslinking agent and monomer styrene are dissolved in a solvent system and then reacted under certain conditions. However, many documents demonstrate that such dispersion polymerization causes flocculation or coagulation during the reaction, so that the reaction mostly ends up failing, and even if everything is normal during the reaction, the product is found to be irregular spheroidal particles and have a wide size distribution during the morphological characterization.
The seed swelling method is a multi-step method for synthesizing crosslinked polystyrene microspheres. Firstly, synthesizing linear polystyrene microspheres as seed microspheres by using methods such as dispersion polymerization, emulsion polymerization and the like, then swelling the seed microspheres for many times by using a swelling agent, a monomer, a cross-linking agent and the like, finally adding a stabilizing agent, and completing the reaction under certain conditions. Although the seed swelling method can prepare the crosslinked polystyrene microspheres with larger particle size, the steps involved in the reaction process are too many, and the size distribution of the microspheres is difficult to control. Meanwhile, the seed swelling method has long reaction period and low yield, and is not the best method for synthesizing the crosslinked polystyrene microspheres.
Disclosure of Invention
The invention aims to solve the problems of flocculation phenomenon, multiple steps and long period in the prior art and provides a method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres comprises the following steps:
dissolving a dispersing agent in a mixed medium of alcohol and water under nitrogen to form a homogeneous solution;
adding an initiator and styrene into the homogeneous solution, and uniformly dispersing to obtain a mixed system;
and (3) dropwise adding a cross-linking agent alcohol solution into the mixed system at the temperature of 60-80 ℃, and reacting for 8-48 h at the temperature of 60-80 ℃ after dropwise adding to obtain the micron-sized monodisperse cross-linked polystyrene microspheres.
Furthermore, a dispersion aid is added into the homogeneous solution, and the dosage of the dispersion aid is 1-10% of the mass of the styrene.
Further, the auxiliary dispersing agent is one or more of ascorbic acid, fatty alcohol-polyoxyethylene ether and sodium dodecyl diphenyl ether disulfonate.
Further, the alcohol in the alcohol and water mixed medium is one or more of ethanol, isopropanol and ethylene glycol;
the mass ratio of the alcohol to the water is 70-110: 5.
Further, the dispersing agent is one or more of polyvinylpyrrolidone, hydroxypropyl cellulose, polyacrylic acid and polyethylene glycol;
the dosage of the dispersant is 10-30% of the mass of the styrene.
Furthermore, the dosage of the styrene is 10 to 30 percent of the mass of the mixed medium of the alcohol and the water.
Further, the initiator is one or more of azodiisobutyronitrile, benzoyl peroxide and lauroyl peroxide;
the dosage of the initiator is 1 to 5 percent of the mass of the styrene.
Further, the crosslinking agent is divinylbenzene.
Furthermore, the dosage of the cross-linking agent is 0.3 to 15 percent of the mass of the styrene.
Furthermore, the dripping time of the cross-linking agent alcohol solution is 1-6 h.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the methods of dispersion polymerization and dripping the cross-linking agent, can control the content of the cross-linking agent at an extremely low concentration, thereby effectively inhibiting the condition of irregular growth of the microspheres caused by different reactivity ratios, simultaneously effectively avoiding flocculation phenomenon in the traditional dispersion polymerization process, enabling the microspheres to uniformly grow, and finally preparing the microsphere product with uniform particle size distribution and good sphericity. Compared with the seed swelling method which adopts seed ball preparation, then swelling of swelling agent, monomer and cross-linking agent in multiple steps, and finally carrying out polymerization reaction in multiple steps and complicated operations, the method can prepare the micron-sized monodisperse cross-linked polystyrene microspheres in one step, and has high preparation efficiency. The invention can prepare the crosslinked polystyrene microspheres with monodispersity, good sphericity and particle size of 1.20-3.68 mu m, and can be widely applied to the fields of spacers, biomedicine, standard measurement, chemical synthesis, microelectronics and the like.
Drawings
FIG. 1 is an electron micrograph of polystyrene microspheres prepared in example 1 of the present invention.
FIG. 2 is an electron micrograph of polystyrene microspheres prepared in example 2 of the present invention.
FIG. 3 is an electron micrograph of polystyrene microspheres prepared in example 3 of the present invention.
FIG. 4 is an electron micrograph of polystyrene microspheres prepared in example 4 of the present invention.
FIG. 5 is an electron micrograph of polystyrene microspheres prepared in example 5 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific examples.
The invention relates to a method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres, which comprises the following steps:
step 1, dissolving a dispersing agent and an auxiliary dispersing agent or dissolving the dispersing agent in a mixed medium of alcohol and water, forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen into the homogeneous solution to discharge oxygen in the homogeneous solution; wherein, the alcohol in the mixed medium of alcohol and water is one or more of ethanol, isopropanol and glycol, and the mass ratio of the alcohol to the water is 70-110: 5.
The dispersant is one or more of polyvinylpyrrolidone, hydroxypropyl cellulose, polyacrylic acid, polyethylene glycol, etc.
The auxiliary dispersing agent is one or more of ascorbic acid, fatty alcohol-polyoxyethylene ether, sodium dodecyl diphenyl ether disulfonate and the like.
The dosage of the dispersant is 10-30% of the mass of the styrene;
the dosage of the auxiliary dispersant is 1 to 10 percent of the mass of the styrene.
Step 2, adding an initiator and styrene into the solution obtained in the step 1, and uniformly dispersing under mechanical stirring at the speed of 150-300 r/min to obtain a mixed system; wherein, the dosage of the styrene is 10 to 30 percent of the mass of the solvent (alcohol and water mixed medium).
The initiator is one or more of azodiisobutyronitrile, benzoyl peroxide, lauroyl peroxide and the like, and the dosage of the initiator is 1-5% of the mass of the styrene.
And 3, dissolving the cross-linking agent in alcohol to prepare a homogeneous solution. Wherein the crosslinking agent is divinyl benzene, and the using amount of the crosslinking agent is 0.3-15% of the mass of styrene; wherein the alcohol is the same as the alcohol in the mixed medium of the alcohol and the water in the step 1.
And 4, heating the solution system obtained in the step 2 to 60-80 ℃, starting to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the reaction system, and keeping the temperature at 60-80 ℃ for 8-48 h after dropwise adding is finished, thus finishing the reaction. Wherein the dripping time of the cross-linking agent alcoholic solution is 1-6 h.
And 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain a polystyrene microsphere product.
In the method, the nitrogen atmosphere is kept in the whole reaction process, and condensed water is communicated.
In order to further illustrate the above scheme, several specific examples are given below. These examples are intended to further illustrate the features and advantages of the present invention and are not intended to limit the scope of the present invention.
Example 1
Step 1, dissolving 2.5g of polyvinylpyrrolidone in 5mL of deionized water and 100mL of absolute ethyl alcohol, forming a homogeneous solution by ultrasonic treatment, and continuously introducing nitrogen into the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, respectively adding 0.75g of azobisisobutyronitrile and 16.5mL of styrene into the solution obtained in the step 1, and uniformly mixing at a stirring speed of 220r/min to obtain a mixed system;
step 3, dissolving 163 mu L of cross-linking agent divinylbenzene in 22mL of absolute ethyl alcohol to prepare a homogeneous solution, so as to obtain a cross-linking agent solution;
step 4, heating the mixed system obtained in the step 2 to 75 ℃, then dropwise adding the cross-linking agent solution obtained in the step 3 for 4 hours, and after the dropwise adding is finished, keeping the temperature of 75 ℃ for 8 hours to complete the reaction;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
As can be seen from FIG. 1, the average particle size of the product prepared in this example is 1.26 μm, the sphericity is good, and the coefficient of variation is 0.016.
Example 2
Step 1, dissolving 2.5g of polyvinylpyrrolidone in 5mL of deionized water and 110mL of absolute ethyl alcohol, forming a homogeneous solution by ultrasonic treatment, and continuously introducing nitrogen into the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, respectively adding 0.75g of azobisisobutyronitrile and 16.5mL of styrene into the solution obtained in the step 1, and uniformly mixing at a stirring speed of 220r/min to obtain a mixed system;
step 3, dissolving 163 mu L of cross-linking agent divinylbenzene in 12mL of absolute ethyl alcohol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 70 ℃, starting to dropwise add the cross-linking agent solution obtained in the step 3 into the mixed system, keeping the time for 6 hours, and finishing the reaction at the constant temperature of 70 ℃ for 24 hours after the dropwise addition;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
As can be seen from FIG. 2, the average particle size of the product prepared in this example was 1.36. Mu.m, the sphericity was good, and the coefficient of variation was 0.014.
Example 3
Step 1, dissolving 2.5g of polyvinylpyrrolidone in 5mL of deionized water and 110mL of absolute ethyl alcohol, forming a homogeneous solution by ultrasonic treatment, and continuously introducing nitrogen into the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, respectively adding 0.50g of azobisisobutyronitrile and 16.5mL of styrene into the solution obtained in the step 1, and uniformly mixing at a stirring speed of 220r/min to obtain a mixed system;
step 3, dissolving 163 mu L of cross-linking agent divinylbenzene in 12mL of absolute ethyl alcohol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 70 ℃, starting to dropwise add the cross-linking agent solution obtained in the step 3 into the mixed system, keeping the time for 6 hours, and finishing the reaction at the constant temperature of 70 ℃ for 24 hours after the dropwise addition;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
As can be seen from FIG. 3, the average particle size of the product prepared in this example was 1.20. Mu.m, the sphericity was good, and the coefficient of variation was 0.014.
Example 4
Step 1, dissolving 2.0g of polyvinylpyrrolidone in 5mL of deionized water and 115mL of isopropanol, forming a homogeneous solution by ultrasonic treatment, and continuously introducing nitrogen into the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, respectively adding 0.75g of azobisisobutyronitrile and 16.5mL of styrene into the solution obtained in the step 1, and uniformly mixing at a stirring speed of 220r/min to obtain a mixed system;
step 3, dissolving 1.63mL of cross-linking agent divinylbenzene into 6mL of isopropanol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 66 ℃, starting to dropwise add the cross-linking agent solution obtained in the step 3 into the mixed system, keeping the time for 6 hours, and finishing the reaction at the constant temperature of 66 ℃ for 24 hours after the dropwise addition;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
As can be seen from FIG. 4, the average particle size of the product prepared in this example is 1.83 μm, the sphericity is good, and the coefficient of variation is 0.013.
Example 5
Step 1, dissolving 2.3g of hydroxypropyl cellulose in 140mL of isopropanol and 5mL of deionized water, forming a homogeneous solution by ultrasonic dispersion, and continuously introducing nitrogen into the solution to discharge oxygen in the solution;
step 2, after nitrogen is introduced for about 30min, respectively adding 0.69g of azobisisobutyronitrile and 25mL of styrene into the solution obtained in the step 1, and uniformly mixing under mechanical stirring at the speed of 150r/min to obtain a mixed system;
step 3, dissolving 75 mu L of cross-linking agent divinylbenzene into 5mL of isopropanol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 60 ℃, starting to dropwise add the cross-linking agent solution obtained in the step 3 into the reaction system, continuing the dropwise adding process for 1h, and finishing the reaction at the constant temperature of 60 ℃ for 48h after the dropwise adding process is finished;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
As can be seen from FIG. 5, the average particle size of the product prepared by this example is 1.48 μm, the sphericity is good, and the coefficient of variation is 0.017.
Example 6
Step 1, dissolving 1.15g of polyvinylpyrrolidone, 1g of polyethylene glycol and 1.4g of fatty alcohol-polyoxyethylene ether in an alcohol-water mixed medium (90 mL of ethanol, 25mL of isopropanol and 5mL of water), forming a homogeneous solution by ultrasonic dispersion, and continuously introducing nitrogen to discharge oxygen in the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, adding 0.3g of initiator (wherein, azodiisobutyronitrile is 0.15g, benzoyl peroxide is 0.15 g) and 16mL of styrene into the solution obtained in the step 1, and uniformly mixing under mechanical stirring at the speed of 250r/min to obtain a mixed system;
step 3, dissolving 2.4mL of cross-linking agent divinylbenzene in 10mL of ethanol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 65 ℃, beginning to dropwise add the cross-linking agent solution obtained in the step 3 into the mixed system, keeping the time for 3 hours, and keeping the temperature at 65 ℃ for 32 hours after dropwise adding is finished, so as to finish the reaction;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
The product prepared in this example had an average particle size of 2.60 μm, good sphericity and a coefficient of variation of 0.030.
Example 7
Step 1, dissolving 6.75g of polyacrylic acid in 90mL of isopropanol and 5mL of deionized water, forming a homogeneous solution by ultrasonic dispersion, and continuously introducing nitrogen to discharge oxygen in the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, adding 1.12g of benzoyl peroxide and 24.8mL of styrene into the solution obtained in the step 1, and uniformly mixing under mechanical stirring at the speed of 200r/min to obtain a mixed system;
step 3, dissolving 1.2mL of cross-linking agent divinylbenzene in 20mL of isopropanol to prepare a homogeneous solution, so as to obtain a cross-linking agent alcoholic solution;
step 4, heating the solution system obtained in the step 2 to 70 ℃, beginning to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the mixed system, keeping the time for 6 hours, and keeping the temperature at 70 ℃ for 20 hours after dropwise adding is finished, so as to finish the reaction;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
The average particle size of the product prepared by the embodiment is 3.68 μm, the sphericity is good, and the coefficient of variation is 0.017.
Example 8
Step 1, dissolving 1.3g of polyacrylic acid, 1g of polyethylene glycol and 1.15g of ascorbic acid in 100mL of ethylene glycol and 5mL of deionized water, forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen into the homogeneous solution to discharge oxygen in the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, adding 0.115g of lauroyl peroxide and 12.7mL of styrene into the solution obtained in the step 1, and uniformly mixing under mechanical stirring at the speed of 300r/min to obtain a mixed system;
step 3, dissolving 1.25mL of cross-linking agent divinylbenzene in 10mL of glycol to prepare a homogeneous solution;
step 4, heating the solution system obtained in the step 2 to 80 ℃, beginning to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the mixed system, keeping the time for 3 hours, and keeping the temperature at 80 ℃ for 8 hours after dropwise adding is finished, so as to finish the reaction;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
The average particle size of the product prepared by the embodiment is 2.72 μm, the sphericity is good, and the coefficient of variation is 0.016.
Example 9
Step 1, dissolving a dispersing agent (2.5 g of polyvinylpyrrolidone, 2g of hydroxypropyl cellulose and 2g of polyethylene glycol) and an auxiliary dispersing agent (1.3 g of sodium dodecyl diphenyl ether disulfonate and 1.3g of fatty alcohol-polyoxyethylene ether) in an alcohol-water mixed medium (wherein the mixed medium is 86mL of ethanol, 20mL of isopropanol, 15mL of ethylene glycol and 5mL of deionized water), forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen to discharge oxygen in the homogeneous solution;
step 2, after nitrogen is introduced for about 30min, adding 1.05g of initiator (0.55 g of benzoyl peroxide and 0.5g of lauroyl peroxide) and 28.9mL of styrene into the solution obtained in the step 1, and uniformly mixing under mechanical stirring at the speed of 270r/min to obtain a mixed system;
step 3, dissolving 2.8mL of cross-linking agent divinylbenzene in 15mL of ethanol to prepare a homogeneous solution, so as to obtain a cross-linking agent alcoholic solution;
step 4, heating the solution system obtained in the step 2 to 75 ℃, beginning to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the mixed system, keeping the time for 6 hours, and keeping the temperature at 75 ℃ for 15 hours after dropwise adding is finished, so as to finish the reaction;
and 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
The average particle size of the product prepared by the embodiment is 1.50 μm, the sphericity is good, and the coefficient of variation is 0.025.
Example 10
Step 1, dissolving a dispersing agent (2 g) and an auxiliary dispersing agent in a mixed medium of alcohol and water, forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen into the homogeneous solution to discharge oxygen in the homogeneous solution; wherein the alcohol in the alcohol and water mixed medium is ethanol, and the mass ratio of the alcohol to the water is 70: 5.
The dispersant is polyvinylpyrrolidone.
The dispersion aid is ascorbic acid.
The dosage of the dispersant is 10 percent of the mass of the styrene;
the dosage of the auxiliary dispersant is 5 percent of the mass of the styrene.
Step 2, adding an initiator and styrene into the solution obtained in the step 1, and dispersing uniformly under the mechanical stirring at the speed of 150r/min to obtain a mixed system; wherein, the dosage of the styrene is 20 percent of the mass of the solvent (alcohol and water mixed medium).
The initiator is azobisisobutyronitrile, and the using amount of the initiator is 1% of the mass of the styrene.
And 3, dissolving the cross-linking agent in alcohol to prepare a homogeneous solution, thereby obtaining the cross-linking agent alcohol solution. Wherein the crosslinking agent is divinylbenzene, and the using amount of the crosslinking agent is 8 percent of the mass of styrene; wherein the alcohol is the same as the alcohol in the mixed medium of the alcohol and the water in the step 1.
And 4, heating the solution system obtained in the step 2 to 60 ℃, starting to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the reaction system, and keeping the temperature at 60 ℃ for 48 hours after dropwise adding is finished, so as to finish the reaction. Wherein the dripping time of the cross-linking agent alcoholic solution is 1h.
And 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
Example 11
Step 1, dissolving a dispersing agent (2 g) and an auxiliary dispersing agent in a mixed medium of alcohol and water, forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen to discharge oxygen in the homogeneous solution; wherein the alcohol in the alcohol and water mixed medium is isopropanol, and the mass ratio of the alcohol to the water is 110: 5.
The dispersing agent is hydroxypropyl cellulose.
The auxiliary dispersing agent is fatty alcohol-polyoxyethylene ether.
The using amount of the dispersing agent is 30 percent of the mass of the styrene;
the dosage of the auxiliary dispersant is 1 percent of the mass of the styrene.
Step 2, adding an initiator and styrene into the solution obtained in the step 1, and dispersing uniformly under mechanical stirring at the speed of 200r/min to obtain a mixed system; wherein, the dosage of the styrene is 10 percent of the mass of the solvent (alcohol and water mixed medium).
The initiator is benzoyl peroxide and lauroyl peroxide, and the dosage of the initiator is 5 percent of the mass of the styrene.
And 3, dissolving the cross-linking agent in alcohol to prepare a homogeneous solution. Wherein the crosslinking agent is divinylbenzene, and the using amount of the crosslinking agent is 15 percent of the mass of styrene; wherein the alcohol is the same as the alcohol in the mixed medium of the alcohol and the water in the step 1.
And 4, heating the solution system obtained in the step 2 to 80 ℃, starting to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the reaction system, and keeping the temperature at 80 ℃ for 8 hours after dropwise adding is finished, so as to finish the reaction. Wherein the dripping time of the cross-linking agent alcoholic solution is 6h.
And 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
Example 12
Step 1, dissolving a dispersing agent (2 g) and an auxiliary dispersing agent in a mixed medium of alcohol and water, forming a homogeneous solution through ultrasonic dispersion, and continuously introducing nitrogen to discharge oxygen in the homogeneous solution; wherein the alcohol in the alcohol and water mixed medium is a mixture of isopropanol and glycol, and the mass ratio of the alcohol to the water is 90: 5.
The dispersant is a mixture of polyacrylic acid and polyethylene glycol.
The auxiliary dispersing agent is a mixture of fatty alcohol-polyoxyethylene ether and sodium dodecyl diphenyl ether disulfonate.
The using amount of the dispersing agent is 20 percent of the mass of the styrene;
the dosage of the auxiliary dispersant is 10 percent of the mass of the styrene.
Step 2, adding an initiator and styrene into the solution obtained in the step 1, and uniformly dispersing under the mechanical stirring at the speed of 300r/min to obtain a mixed system; wherein, the dosage of the styrene is 30 percent of the mass of the solvent (alcohol and water mixed medium).
The initiator is a mixture of benzoyl peroxide and lauroyl peroxide, and the dosage of the initiator is 3 percent of the mass of the styrene.
And 3, dissolving the cross-linking agent in alcohol to prepare a homogeneous solution. Wherein the crosslinking agent is divinylbenzene, and the using amount of the crosslinking agent is 0.3 percent of the mass of styrene; wherein the alcohol is the same as the alcohol in the mixed medium of the alcohol and the water in the step 1.
And 4, heating the solution system obtained in the step 2 to 70 ℃, starting to dropwise add the cross-linking agent alcohol solution obtained in the step 3 into the reaction system, and keeping the temperature at 70 ℃ for 30 hours after dropwise adding is finished, so as to finish the reaction. Wherein the dripping time of the cross-linking agent alcoholic solution is 3h.
And 5, centrifuging, washing and drying the reaction liquid obtained in the step 4 to obtain the micron-sized monodisperse crosslinked polystyrene microspheres.
The invention can prepare the crosslinked polystyrene microsphere with monodispersity, good sphericity and 1.2-3.68 mu m particle size, and the polystyrene microsphere can be widely applied to the fields of spacers, biomedicine, standard measurement, chemical synthesis, microelectronics and the like.
Claims (10)
1. A method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres is characterized by comprising the following steps:
dissolving a dispersing agent in a mixed medium of alcohol and water under nitrogen to form a homogeneous solution; adding an initiator and styrene into the homogeneous solution, and uniformly dispersing to obtain a mixed system; and (3) dropwise adding a cross-linking agent alcohol solution into the mixed system at the temperature of 60-80 ℃, and reacting for 8-48 h at the temperature of 60-80 ℃ after dropwise adding to obtain the micron-sized monodisperse cross-linked polystyrene microspheres.
2. The method for directly preparing the micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the dispersion aid is added into the homogeneous solution, and the amount of the dispersion aid is 1-10% of the mass of the styrene.
3. The method of claim 2, wherein the auxiliary dispersant is one or more selected from ascorbic acid, fatty alcohol-polyoxyethylene ether and sodium dodecyl diphenyl ether disulfonate.
4. The method for directly preparing the micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the alcohol in the alcohol-water mixed medium is one or more of ethanol, isopropanol and ethylene glycol;
the mass ratio of the alcohol to the water is 70-110: 5.
5. The method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the dispersant is one or more of polyvinylpyrrolidone, hydroxypropyl cellulose, polyacrylic acid and polyethylene glycol;
the dosage of the dispersant is 10-30% of the mass of the styrene.
6. The method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the amount of styrene used is 10-30% by mass of the mixed medium of alcohol and water.
7. The method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the initiator is one or more of azobisisobutyronitrile, benzoyl peroxide and lauroyl peroxide;
the dosage of the initiator is 1 to 5 percent of the mass of the styrene.
8. The method for directly preparing the micron-sized monodisperse crosslinked polystyrene microspheres of claim 1, wherein the crosslinking agent is divinylbenzene.
9. The method for directly preparing the micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the amount of the crosslinking agent is 0.3-15% by mass of styrene.
10. The method for directly preparing micron-sized monodisperse crosslinked polystyrene microspheres according to claim 1, wherein the dripping time of the crosslinking agent alcohol solution is 1-6 h.
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