CN112516930B - Method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance - Google Patents
Method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance Download PDFInfo
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Abstract
The invention discloses a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance, which comprises the following steps: preparing a continuous phase solution; preparing a dispersed phase solution; preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes dispersed phase solution as an O phase and takes continuous phase solution as W2 phase solution; collecting W1/O/W2 composite emulsion particles by using a cylindrical bottle filled with a polyvinyl alcohol aqueous solution, and placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles to obtain poly-alpha-methylstyrene microspheres internally sealed with a W1 phase; and (2) placing the poly-alpha-methylstyrene microspheres in distilled water for washing, placing the washed poly-alpha-methylstyrene microspheres in ethanol for soaking, picking out the microspheres and placing the microspheres in a vacuum oven for drying to obtain the poly-alpha-methylstyrene hollow microspheres. The preparation method of the invention improves the sphericity and surface smoothness of the PAMS hollow microspheres; the degradation temperature of the microspheres is reduced, and the complete degradation of the PAMS microspheres is promoted.
Description
Technical Field
The invention belongs to the field of polymer processing and forming, and particularly relates to a preparation method of degradable polymer micro hollow microspheres with high sphericity and surface finish.
Background
The inertial confinement fusion realizes implosion by bombarding a target pill loaded with deuterium-tritium fuel with strong laser to obtain fusion energy, is an effective means most expected to realize controllable thermonuclear fusion, and has very important strategic significance in the fields of national defense safety and novel clean energy. In the physical experiment of the implosion, the uniform and symmetrical compression of the nuclear fuel is a necessary premise for successfully realizing the nuclear fusion, so the physical experiment of the inertial confinement fusion puts very strict requirements on the sphericity and the surface finish of the fuel target pellet. Among the target pellets of various materials, Glow Discharge Polymer (GDP) target pellets are favored by ICF physical experiments because they have the properties of low mass, low density, etc. to effectively reduce the hydrodynamic instability during implosion.
The preparation process of the GDP target pill is shown in figure 7: firstly, preparing poly-alpha-methyl styrene (PAMS) hollow microspheres; depositing a uniform hydrocarbon coating on the PAMS microspheres by a low-pressure plasma chemical vapor deposition method to obtain PAMS/GDP composite microspheres; finally, the PAMS microspheres are degraded and removed by using a thermal degradation technology to obtain the GDP target pills. From the above process, it can be seen that, in the preparation process of the GDP target pellet, the PAMS hollow microspheres play a role of a template, the sphericity and the surface smoothness of the PAMS hollow microspheres directly affect the sphericity and the surface quality of the GDP target pellet, and in addition, the degradation performance of the PAMS hollow microspheres also seriously affects the inner surface quality of the GDP target pellet. Therefore, the synchronous improvement of the sphericity, the surface quality and the degradation performance of the PAMS hollow microspheres has important significance for the preparation of high-quality GDP target pills.
At present, the emulsion micro-encapsulation technology is a main method for preparing PAMS hollow microspheres, and the preparation process comprises the steps of constructing W1/O/W2 composite emulsion particles by utilizing a micro-fluidic channel; carrying out rotary evaporation and solidification on the composite emulsion particles to obtain hardened microspheres; and drying the hardened microspheres, and removing the internal water phase to obtain the PAMS hollow microspheres. However, in the process of rotary evaporation curing, due to the shearing action of the rotary flow field on the W1/O/W2 composite emulsion particles and the Marangoni convection action of the O-W2 interface, the composite emulsion particles are easy to deform in the curing process, and the outer surface of the composite emulsion particles has concave-convex fluctuation, so that the sphericity and the surface quality of the PAMS microspheres after curing are seriously affected, and the quality and the preparation efficiency of the GDP target pellet are finally affected. In order to realize the quality improvement and efficiency improvement of the preparation of the GDP target pellets and the PAMS hollow microspheres, the invention starts from the preparation process of the PAMS hollow microspheres, fully regulates and controls the solidification process of milk particles by introducing the di-tert-butyl peroxide into a dispersion phase, realizes the great increase of the sphericity of the solidified PAMS hollow microspheres, and further realizes the further increase of the surface quality of the PAMS microspheres by optimizing the addition concentration of the di-tert-butyl peroxide. Meanwhile, due to the addition of di-tert-butyl peroxide, the degradation temperature of the PAMS hollow microspheres can be effectively reduced, the complete degradation of the PAMS microspheres is promoted, and the improvement of the quality of the GDP target pellet is finally facilitated.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing high sphericity, high surface smoothness, high degradation performance hollow microspheres comprising the steps of:
step one, preparing a continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1-2 hours at 80-90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 1-3%;
step two, preparing a dispersed phase solution: preparing a poly-alpha-methylstyrene solution with the mass concentration of 10-13% by using fluorobenzene as a solvent, adding di-tert-butyl peroxide into the solution, and continuously stirring for 45-52 hours; wherein, the mass concentration of the di-tert-butyl peroxide in the poly-alpha-methylstyrene solution is 1 to 5 percent;
step three, preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the step two as an O phase, and takes the continuous phase solution prepared in the step one as a W2 phase solution;
collecting the W1/O/W2 composite emulsion particles by using a cylindrical bottle filled with a polyvinyl alcohol aqueous solution, putting the composite emulsion particles into a water-bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, and solidifying for 45-52 hours to obtain poly-alpha-methylstyrene microspheres internally sealed with a W1 phase;
and fifthly, placing the poly-alpha-methylstyrene microspheres obtained in the fourth step into distilled water for repeated washing, placing the washed poly-alpha-methylstyrene microspheres into ethanol for soaking for 7 days, picking out the microspheres floating in the ethanol, and placing the microspheres in a vacuum oven for drying for 45-52 hours to obtain the poly-alpha-methylstyrene hollow microspheres.
Preferably, the assembly method of the three-dimensional coaxial microfluidic channel comprises the following steps: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; and fixing and assembling the capillaries into the three-dimensional coaxial microfluidic channel by AB epoxy resin glue.
Preferably, the molecular weight of the polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%; the poly-alpha-methylstyrene has a molecular weight of 280000g/mol and a molecular weight distribution of less than 1.01.
Preferably, in the third step, the three-phase flow rates of the W1/O/W2 composite emulsion particles prepared by using the three-dimensional coaxial microfluidic channels are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter is 920 mu m.
Preferably, in the fourth step, the amount of the polyvinyl alcohol aqueous solution contained in the cylindrical bottle is 200 mL; the number of the collected W1/O/W2 composite emulsion particles was 200, and the water bath temperature of the rotary evaporation device was set to 30 ℃ at a rotation speed of 25 rpm.
Preferably, in the fourth step, the poly-alpha-methylstyrene microspheres encapsulated with the W1 phase are obtained after curing for 45-52 hours, wherein the sphere inner diameter is 700 μm, and the outer diameter is 740 μm.
Preferably, in the fifth step, the drying temperature is 45 ℃.
Preferably, in the second step, fluorobenzene is used as a solvent, a poly-alpha-methylstyrene solution with the mass concentration of 10-13% is prepared, di-tert-butyl peroxide is added into the poly-alpha-methylstyrene solution, the poly-alpha-methylstyrene solution is stirred in a spiral magnetic field for 8-12 hours, and then the poly-alpha-methylstyrene solution is subjected to pressure ultrasonic treatment for 3-5 hours; wherein the mass concentration of the di-tert-butyl peroxide in the poly-alpha-methylstyrene solution is 1-5%.
Preferably, the stirring speed in the spiral magnetic field is 80-150 r/min, the stirring mode is 15-25 min clockwise and 15-25 min anticlockwise; the magnetic field intensity is 1T-5T.
Preferably, the pressure of the pressure ultrasonic treatment is 0.4-1.2 MPa, and the frequency is 45-65 KHz. .
The invention at least comprises the following beneficial effects: the preparation method of the invention improves the sphericity and surface smoothness of the PAMS hollow microspheres; the degradation temperature of the microspheres is reduced, and the complete degradation of the PAMS microspheres is promoted.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an optical microscope photograph of the PAMS hollow microsphere prepared in example 1 of the present invention and a white light interference image of the external surface morphology of the microsphere;
FIG. 2 is an optical microscope photograph of the PAMS hollow microsphere prepared in example 2 of the present invention and a white light interference image of the outer surface morphology of the microsphere;
FIG. 3 is an optical microscope photograph of the PAMS hollow microsphere prepared in example 3 of the present invention and a white light interference image of the outer surface morphology of the microsphere;
FIG. 4 is an optical micrograph of a GDP target pellet prepared using the PAMS hollow microspheres of example 2 according to the present invention;
FIG. 5 is a photomicrograph of the PAMS hollow microspheres prepared in comparative example 1 of the present invention and a white light interference image of the external surface morphology of the microspheres;
FIG. 6 is an optical microscope photograph of GDP target pellets prepared using PAMS hollow microspheres of comparative example 1 in accordance with the present invention;
FIG. 7 is a schematic diagram of the preparation of GDP target pellet.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, and continuously stirring for 48 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 1 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the third step as an O phase, and takes the continuous phase solution prepared in the second step as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution (namely continuous phase solution), placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify a composite emulsion particle oil layer liquid film, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres. FIG. 1 shows an optical microscope photograph of the PAMS hollow microsphere with high sphericity and surface finish prepared in this example and a white light interference image of the external surface morphology of the microsphere;
example 2:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, and continuously stirring for 48 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 3 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; it is composed ofIn the W1/O/W2 composite emulsion particles, deionized water is used as a W1 phase, the dispersed phase solution prepared in the step three is used as an O phase, and the continuous phase solution prepared in the step two is used as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres. FIG. 2 shows an optical microscope photograph of the PAMS hollow microsphere with high sphericity and surface finish prepared in this example and a white light interference image of the external surface morphology of the microsphere; FIG. 4 shows an optical microscope photograph of GDP target pellets prepared using the PAMS hollow microspheres; as can be seen from the figure, PAMS microspheres degraded completely without PAMS residue.
Example 3:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, and continuously stirring for 48 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 5 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the third step as an O phase, and takes the continuous phase solution prepared in the second step as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres. FIG. 3 shows an optical microscope photograph of the PAMS hollow microsphere with high sphericity and surface finish prepared in this example and a white light interference image of the external surface morphology of the microsphere;
comparative example 1:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, and continuously stirring for 48 hours; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the third step as an O phase, and takes the continuous phase solution prepared in the second step as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres. FIG. 5 shows an optical microscope photograph of the PAMS hollow microsphere prepared in this example and a white light interference image of the external surface morphology of the microsphere; FIG. 6 shows an optical microscope photograph of GDP target pellets prepared using the PAMS hollow microspheres; as can be seen from the figure, incomplete degradation of PAMS microspheres resulted in PAMS residues on the inner surface of the target pellet.
Example 4:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, stirring the PAMS solution in a spiral magnetic field for 12 hours, and then carrying out pressure ultrasonic treatment for 5 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 1 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01; stirring in a spiral magnetic field at a speed of 100r/min in a clockwise manner for 25min and a counterclockwise manner for 25 min; the magnetic field intensity is 3T; the pressure of the pressure ultrasonic treatment is 0.8MPa, and the frequency is 50 KHz; through the action of a spiral magnetic field and pressurized ultrasound, the mixture of the di-tert-butyl peroxide and the PAMS is more uniform and stable, and the prepared PAMS hollow microspheres have more excellent performance.
Preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the step three as an O phase,taking the continuous phase solution prepared in the step two as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres.
Example 5:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, stirring the PAMS solution in a spiral magnetic field for 12 hours, and then carrying out pressure ultrasonic treatment for 5 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 3 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01; stirring in a spiral magnetic field at a speed of 100r/min in a clockwise manner for 25min and a counterclockwise manner for 25 min; the magnetic field intensity is 3T; the pressure of the pressure ultrasonic treatment is 0.8MPa, and the frequency is 50 KHz;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the third step as an O phase, and takes the continuous phase solution prepared in the second step as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres.
Example 6:
a method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance comprises the following steps:
step one, assembling a three-dimensional coaxial microfluidic channel: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; fixing and assembling each capillary tube into a three-dimensional coaxial microfluidic channel by AB epoxy resin adhesive;
step two, preparing continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1 hour at 90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 2%; the molecular weight of the adopted polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%;
step three, preparing a dispersed phase solution: preparing a PAMS solution with the mass concentration of 12% by taking fluorobenzene as a solvent, adding di-tert-butyl peroxide into the PAMS solution, stirring the PAMS solution in a spiral magnetic field for 12 hours, and then carrying out pressure ultrasonic treatment for 5 hours; wherein the mass concentration of the di-tert-butyl peroxide in the PAMS solution is 5 percent; the molecular weight of the adopted poly-alpha-methylstyrene PAMS is 280000g/mol, and the molecular weight distribution is less than 1.01; stirring in a spiral magnetic field at a speed of 100r/min in a clockwise manner for 25min and a counterclockwise manner for 25 min; the magnetic field intensity is 3T; the pressure of the pressure ultrasonic treatment is 0.8MPa, and the frequency is 50 KHz;
preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the third step as an O phase, and takes the continuous phase solution prepared in the second step as a W2 phase solution; the three-phase flow rates adopted when preparing the W1/O/W2 composite emulsion particles are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter of the composite emulsion particle is 920 mu m;
step five, collecting 200W 1/O/W2 composite emulsion particles by using a cylindrical bottle filled with 200mL of polyvinyl alcohol solution, placing the composite emulsion particles in a water bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, setting the water temperature of a rotary evaporator to be 30 ℃, setting the rotating speed to be 25rpm, and solidifying for 48 hours to obtain PAMS microspheres internally sealed with W1 phases;
and step six, repeatedly washing the PAMS microspheres obtained in the step five in distilled water, soaking the washed PAMS microspheres in ethanol for 7 days, picking out the microspheres floating in the ethanol, and drying in a vacuum oven at 45 ℃ for 48 hours to obtain the PAMS hollow microspheres.
Measurement statistics are carried out on the yield of the PAMS hollow microspheres prepared in examples 1-6 and comparative example 1, wherein the spherical deviation of the PAMS hollow microspheres is less than 2 μm, the surface roughness of the microspheres and the thermal degradation temperature of the microspheres, and the results are shown in Table 1;
TABLE 1
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (6)
1. A method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance is characterized by comprising the following steps:
step one, preparing a continuous phase solution: preparing a certain amount of polyvinyl alcohol aqueous solution, stirring for 1-2 hours at 80-90 ℃, and filtering with filter paper after constant volume to obtain the polyvinyl alcohol aqueous solution with the mass concentration of 1-3%;
step two, preparing a dispersed phase solution: preparing a poly-alpha-methylstyrene solution with the mass concentration of 10-13% by using fluorobenzene as a solvent, adding di-tert-butyl peroxide into the poly-alpha-methylstyrene solution, stirring the mixture in a spiral magnetic field for 8-12 hours, and then carrying out pressure ultrasonic treatment for 3-5 hours; wherein the mass concentration of the di-tert-butyl peroxide in the poly-alpha-methylstyrene solution is 1-5%; stirring in a spiral magnetic field at a speed of 80-150 r/min in a clockwise manner for 15-25 min and in a counterclockwise manner for 15-25 min; the magnetic field intensity is 1T-5T; the pressure of the pressurized ultrasonic treatment is 0.4-1.2 MPa, and the frequency is 45-65 KHz;
step three, preparing W1/O/W2 composite emulsion particles by using a three-dimensional coaxial microfluidic channel; wherein, the W1/O/W2 composite emulsion particle takes deionized water as a W1 phase, takes the dispersed phase solution prepared in the step two as an O phase, and takes the continuous phase solution prepared in the step one as a W2 phase solution;
collecting the W1/O/W2 composite emulsion particles by using a cylindrical bottle filled with a polyvinyl alcohol aqueous solution, putting the composite emulsion particles into a water-bath rotary evaporation device to evaporate and solidify an oil layer liquid film of the composite emulsion particles, and solidifying for 45-52 hours to obtain poly-alpha-methylstyrene microspheres internally sealed with a W1 phase;
placing the poly-alpha-methylstyrene microspheres obtained in the fourth step into distilled water for repeated washing, placing the washed poly-alpha-methylstyrene microspheres into ethanol for soaking for 7 days, picking out microspheres floating in the ethanol, and placing the microspheres in a vacuum oven for drying for 45-52 hours to obtain poly-alpha-methylstyrene hollow microspheres;
the molecular weight of the polyvinyl alcohol is 13000-23000 g/mol, and the hydrolysis degree is 87-89%; the poly-alpha-methylstyrene has a molecular weight of 280000g/mol and a molecular weight distribution of less than 1.01.
2. The method for preparing the hollow microsphere with high sphericity, surface finish and degradation performance according to claim 1, wherein the assembling method of the three-dimensional coaxial microfluidic channel comprises: a capillary tube with the inner diameter of 300 mu m and the outer diameter of 400 mu m is used as an inner water phase channel; a capillary tube with the inner diameter of 600 mu m and the outer diameter of 840 mu m and subjected to hydrophobic treatment is used as a middle phase channel; a capillary tube with the inner diameter of 1500 mu m and the outer diameter of 1800 mu m is used as a continuous phase channel; and fixing and assembling the capillaries into the three-dimensional coaxial microfluidic channel by AB epoxy resin glue.
3. The method for preparing hollow microspheres with high sphericity, surface finish and degradation performance as claimed in claim 1, wherein in the third step, the three-phase flow rates for preparing W1/O/W2 composite emulsion particles by using three-dimensional coaxial microfluidic channels are respectively as follows: phase W: 1 mL. h-1And O phase: 1 mL. h-1W2 phase: 200 mL. h-1(ii) a The inner diameter of the W1/O/W2 composite emulsion particle is 700 mu m, and the outer diameter is 920 mu mm。
4. The method for preparing hollow microspheres with high sphericity, high surface finish and high degradability as claimed in claim 1, wherein in the fourth step, the amount of the polyvinyl alcohol aqueous solution contained in the cylindrical bottle is 200 mL; the number of the collected W1/O/W2 composite emulsion particles was 200, and the water bath temperature of the rotary evaporation device was set to 30 ℃ at a rotation speed of 25 rpm.
5. The method for preparing hollow microspheres with high sphericity, high surface finish and high degradation performance according to claim 1, wherein in the fourth step, curing is performed for 45-52 hours to obtain poly-alpha-methylstyrene microspheres encapsulated with W1 phase, wherein the inner diameter of the sphere is 700 μm and the outer diameter is 740 μm.
6. The method for preparing hollow microspheres with high sphericity, surface finish and degradation properties according to claim 1, wherein in the fifth step, the drying temperature is 45 ℃.
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