CN109092178B - Method for preparing monodisperse solid-water-oil composite emulsion particles - Google Patents

Method for preparing monodisperse solid-water-oil composite emulsion particles Download PDF

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CN109092178B
CN109092178B CN201810800871.XA CN201810800871A CN109092178B CN 109092178 B CN109092178 B CN 109092178B CN 201810800871 A CN201810800871 A CN 201810800871A CN 109092178 B CN109092178 B CN 109092178B
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composite emulsion
emulsion particles
oil
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CN109092178A (en
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潘大伟
陈强
刘梅芳
杨璨
李波
刘一杨
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Laser Fusion Research Center China Academy of Engineering Physics
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30Micromixers
    • B01F33/301Micromixers using specific means for arranging the streams to be mixed, e.g. channel geometries or dispositions
    • B01F33/3017Mixing chamber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50Mixing liquids with solids
    • B01F23/51Methods thereof
    • B01F23/511Methods thereof characterised by the composition of the liquids or solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50Mixing liquids with solids
    • B01F23/565Mixing liquids with solids by introducing liquids in solid material, e.g. to obtain slurries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30Micromixers
    • B01F33/302Micromixers the materials to be mixed flowing in the form of droplets
    • B01F33/3021Micromixers the materials to be mixed flowing in the form of droplets the components to be mixed being combined in a single independent droplet, e.g. these droplets being divided by a non-miscible fluid or consisting of independent droplets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/23Mixing of laboratory samples e.g. in preparation of analysing or testing properties of materials

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Abstract

The invention discloses a method for preparing monodisperse solid-water-oil composite emulsion particles, which improves the monodispersity of the solid-water-oil composite emulsion particles by adopting a cross flow focusing shearing mode; the concentration of the oil phase solution and the PVA solution is adjusted to realize density matching among three phases of solid, water and oil, so that the yield of the solid-water-oil composite emulsion particles is improved; regulating physical parameters (viscosity of oil phase solution and oil-water interfacial tension) and working condition parameters (flow rate of dispersed phase and continuous phase), controlling the thickness of PVA liquid film layer, and successfully preparing monodisperse solid-water-oil composite emulsion particles with liquid film thickness range of 50-150 microns. The method can be adjusted to change the diameter of the channel of the generator according to the diameter requirement of the target microsphere, and has the advantages of simple operation and wide application range.

Description

Method for preparing monodisperse solid-water-oil composite emulsion particles
Technical Field
The invention belongs to the field of microfluidic preparation of novel materials, and particularly relates to a method for preparing monodisperse solid-water-oil composite emulsion particles.
Background
Due to the special structure of the solid-water-oil composite emulsion particles (water phase is used as an intermediate layer to separate a solid inner core from an outer oil phase), the solid-water-oil composite emulsion particles are widely applied to the fields of microreactors, pharmaceutical industry and laser Inertial Confinement Fusion (ICF). In an ICF physical experiment, because PVA has good permeation resistance to hydrogen, Polystyrene (PS) -polyvinyl alcohol (PVA) double-layer hollow microspheres are widely used as fuel containers. Currently, PS-PVA double-layer spheres are mainly prepared by solidifying solid-water-oil composite emulsion particles. It can be seen that the monodispersity of the solid-water-oil composite emulsion particles and the thickness of the liquid film have important influence on the quality of the PS-PVA double-layer hollow microspheres.
At present, the stirring method is widely applied to the preparation of solid-water-oil composite emulsion particles. Although the method is simple to operate, the thickness of the prepared composite emulsion liquid membrane has a wide distribution range, and the method is low in repeatability and poor in controllability. Therefore, microfluidic technology was developed to construct solid-water-oil composite emulsion particles. Foreign magnetic force is utilized to push the magnetic particles to penetrate through an oil-water interface so as to obtain the solid-water-oil composite emulsion particles. The liquid film of the solid-water-oil composite emulsion particle prepared by the method is very thin, and only magnetic particles can be coated, so that the application field of the solid-water-oil composite emulsion particle is limited. In the prior art, fluid driven particles are used for constructing solid-water-oil composite emulsion particles. In the early stage, the solid-water-oil composite emulsion particles are successfully constructed by adopting a T-shaped device. However, the monodispersity of the solid inner core is not ideal (greatly improved compared with a stirring method) due to the motion behavior of the solid inner core in the T-shaped opening. Based on this, adopt cross flow focus type micro-fluidic device can effectively control the motion action of solid core at the cross mouth. Furthermore, in a cross-flow focusing microfluidic device, the continuous phase may provide a uniform shearing action. The method can be used for successfully constructing the monodisperse solid-water-oil composite emulsion particles.
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 monodisperse solid-water-oil composite emulsion particles, comprising the steps of:
preparing polystyrene hollow microspheres containing internal phase water, namely solid cores, by using a coaxial emulsion particle generator;
step two, preparing the cross flow focusing type micro-fluidic device with the controllable channel diameter by using a pouring method;
step three, preparing a water phase PVA solution and an oil phase solution with certain concentration according to the requirement of the density matching range;
step four, absorbing a plurality of polystyrene hollow microspheres containing internal phase water into a capillary by using an aqueous phase PVA solution; the capillary tube is tightly connected with a vertical main channel of the cross flow focusing type micro-fluidic device, and meanwhile, the oil phase solution is tightly connected with horizontal side channels on two sides of the cross flow focusing type micro-fluidic device through a hose;
controlling the flow rates of the vertical main channel and the horizontal side channels at two sides by using an injection pump, forming a dispersion phase in the vertical main channel and forming a continuous phase in the horizontal side channels at two sides; when the dispersed phase and the continuous phase meet at a cross opening of the cross flow focusing type micro-fluidic device, the dispersed phase is sheared by the continuous phase to form solid-water-oil composite emulsion particles; after the solid-water-oil composite emulsion particles are formed, the solid-water-oil composite emulsion particles are conveyed through a lower-end straight pipeline of the cross flow focusing type micro-fluidic device to obtain the solid-water-oil composite emulsion particles.
Preferably, in the first step, the polystyrene hollow microspheres are replaced by any one of poly-alpha-methylstyrene, styrene-butadiene-styrene or polyacrylonitrile microspheres.
Preferably, the inner diameter of the polystyrene hollow microsphere in the first step is 700-1300 μm, and the deviation of the inner diameter is +/-10 μm.
Preferably, the horizontal side channels at two sides of the cross flow focusing type microfluidic device in the second step are positioned on the same horizontal line, so that the horizontal side channels uniformly act on a dispersed phase, and the monodispersity of the solid-water-oil composite emulsion particles is improved; the diameter of the channel of the cross flow focusing type micro-fluidic device needs to ensure that the ratio of the solid core to the diameter of the pipeline is more than or equal to 0.65 and less than or equal to 0.85.
Preferably, the molecular weight of the PVA in the PVA solution in the third step is 13000-146000; the hydrolysis degree range is 86-99 percent; the mass concentration range is 2-5%; the oil phase solution is a mixture of dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS.
Preferably, the preparation process of the oil phase solution is as follows: taking the volume ratio of 1-3: 1-3: 1-3 of dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS, uniformly stirring, adding 1-hexyl-3-methylimidazolium tetrafluoroborate and cyclopentasiloxane, stirring for 12-24 hours to obtain a mixed solution, and adding the mixed solution into a high-voltage pulse processing chamber to be processed for 60-90 min by using a high-voltage pulse electric field; the parameters of the high-voltage pulse electric field treatment are as follows: the pulse amplitude is 8-15 KV, the pulse frequency is 800-1200 Hz, and the pulse width is 8-12 us; the dosage of the 1-hexyl-3-methylimidazolium tetrafluoroborate is 0.5-1.5% of the mass of the oil phase solution; the dosage of the cyclopentasiloxane is 1-2% of the mass of the oil phase solution.
Preferably, the density matching range in the third step is that the density difference between the solid core and the aqueous phase PVA solution is greater than or equal to-0.005 g/cm30.005g/cm or less3(ii) a The density matching range between the oil phase solution and the water phase PVA solution is more than or equal to-0.008 g/cm3Less than or equal to 0.008g/cm3
Preferably, the inner diameter of the capillary in the fourth step is consistent with the inner diameter of the vertical main channel of the cross-flow focusing type microfluidic device.
Preferably, in the fifth step, the flow rate ratio of the two side horizontal bypass channels is greater than or equal to 0.8.
Preferably, in the first step, the obtained polystyrene hollow microspheres containing internal phase water are pretreated by the following process: adding polystyrene hollow microspheres and hydrogen peroxide into a sealed container with a stirrer, soaking the polystyrene hollow microspheres in the hydrogen peroxide, introducing nitrogen into the container to saturate the feed liquid with nitrogen, and then placing the sealed container in an electron accelerator of 2.5MeV and 40mA for irradiation stirring treatment; the irradiation dose rate adopted by irradiation is 100-200 kGy/h, the irradiation dose is 200-400 kGy, and the stirring speed is 100-200 r/min; the volume concentration of the hydrogen peroxide is 15-45%.
The invention at least comprises the following beneficial effects: the monodispersity of the solid-water-oil composite emulsion particles is improved by adopting a cross flow focusing shearing mode; the concentration of the oil phase and the PVA solution is adjusted to realize the density matching of the solid-water-oil three phases so as to improve the yield of the solid-water-oil composite emulsion particles; regulating physical parameters (viscosity of oil phase solution and oil-water interfacial tension) and working condition parameters (flow rate of dispersed phase and continuous phase), controlling the thickness of PVA liquid film layer, and successfully preparing monodisperse solid-water-oil composite emulsion particles with liquid film thickness range of 50-150 microns. The method for preparing the monodisperse solid-water-oil composite emulsion particles can change the diameter of the channel of the generator according to the requirement of the diameter of the target microspheres, is simple to operate and wide in application range, and can effectively solve the problem of wide thickness size distribution range of a liquid film of the solid-water-oil composite emulsion particles prepared by the existing stirring method.
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 a high-speed photographic image of the formation process of solid-water-oil composite emulsion particles in a cross-flow focusing type microfluidic device according to the present invention;
FIG. 2 is a graph showing a distribution of the liquid film thickness of the solid-water-oil composite emulsion particles obtained in example 2 of the present invention.
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 of preparing monodisperse solid-water-oil composite emulsion particles comprising the steps of:
preparing polystyrene hollow microspheres containing internal phase water, namely solid cores, with the inner diameter of 750 mu m and the wall thickness of 25 mu m by using a coaxial emulsion generator;
step two, preparing a cross flow focusing type micro-fluidic device with the diameters of both the vertical main channel and the horizontal side channel being 1mm by using a pouring method;
step three, preparing PVA solution with molecular weight of 13000, hydrolysis degree of 86% and mass concentration of 2% according to the requirement of density matching range; the volume ratio is 144: 66 of an oil phase solution of DBP and DOS;
step four, absorbing 50 polystyrene hollow microspheres containing internal phase water into a capillary by using an aqueous phase PVA solution; the capillary tube is tightly connected with a vertical main channel of the cross flow focusing type micro-fluidic device, and meanwhile, the oil phase solution is tightly connected with horizontal side channels on two sides of the cross flow focusing type micro-fluidic device through a hose;
controlling the flow rates of the vertical main channel and the horizontal side channels at two sides by using an injection pump, and adjusting the volume flow of the vertical main channel to be 20mL/h and the volume flow of the horizontal side channels to be 20 mL/h; forming a dispersed phase in the vertical main channel and forming a continuous phase in the horizontal side channels at two sides; when the dispersed phase and the continuous phase meet at a cross opening of the cross flow focusing type micro-fluidic device, the dispersed phase is sheared by the continuous phase to form solid-water-oil composite emulsion particles; after the solid-water-oil composite emulsion particles are formed, the solid-water-oil composite emulsion particles are conveyed through a lower-end straight pipeline of the cross flow focusing type micro-fluidic device to obtain the solid-water-oil composite emulsion particles.
The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is distributed between 95 and 135 mu m, and the polydispersity index is 5 percent.
Example 2:
a method of preparing monodisperse solid-water-oil composite emulsion particles comprising the steps of:
preparing polystyrene hollow microspheres containing internal phase water, namely solid cores, with the inner diameter of 800 microns and the wall thickness of 25 microns by using a coaxial emulsion particle generator;
step two, preparing a cross flow focusing type micro-fluidic device with the diameters of both the vertical main channel and the horizontal side channel being 1mm by using a pouring method;
step three, preparing PVA solution with molecular weight of 13000, hydrolysis degree of 86% and mass concentration of 2% according to the requirement of density matching range; the volume ratio is 2:1, an oil phase solution of DBP and DOS;
step four, absorbing 50 polystyrene hollow microspheres containing internal phase water into a capillary by using an aqueous phase PVA solution; the capillary tube is tightly connected with a vertical main channel of the cross flow focusing type micro-fluidic device, and meanwhile, the oil phase solution is tightly connected with horizontal side channels on two sides of the cross flow focusing type micro-fluidic device through a hose;
controlling the flow rates of the vertical main channel and the horizontal side channels at two sides by using an injection pump, and adjusting the volume flow of the vertical main channel to be 40mL/h and the volume flow of the horizontal side channels to be 40 mL/h; forming a dispersed phase in the vertical main channel and forming a continuous phase in the horizontal side channels at two sides; when the dispersed phase and the continuous phase meet at a cross opening of the cross flow focusing type micro-fluidic device, the dispersed phase is sheared by the continuous phase to form solid-water-oil composite emulsion particles; after the solid-water-oil composite emulsion particles are formed, the solid-water-oil composite emulsion particles are conveyed through a lower-end straight pipeline of the cross flow focusing type micro-fluidic device to obtain the solid-water-oil composite emulsion particles.
The geometric dimension test result shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is distributed between 85 and 125 mu m, and the polydispersity index is 7 percent as shown in figure 2; wherein the calculation formula of the polydispersity index is as follows:
=SD/dav
wherein S isDIs the standard deviation of the thickness of the sample liquid film, davIs the average liquid film thickness; assuming a sample liquid film thickness of x1,x2,x3,xNN numbers, the standard deviation calculation formula is:
Figure BDA0001737058770000061
example 3:
a method of preparing monodisperse solid-water-oil composite emulsion particles comprising the steps of:
preparing polystyrene hollow microspheres containing internal phase water, namely solid cores, with the inner diameter of 850 mu m and the wall thickness of 25 mu m by using a coaxial emulsion particle generator;
step two, preparing a cross flow focusing type micro-fluidic device with the diameters of both the vertical main channel and the horizontal side channel being 1mm by using a pouring method;
step three, preparing a PVA solution with the molecular weight of 15000, the hydrolysis degree of 90 percent and the mass concentration of 3 percent according to the requirement of the density matching range; an oil phase solution of DBP, DOP and DOS in a volume ratio of 2:1: 1;
step four, absorbing 50 polystyrene hollow microspheres containing internal phase water into a capillary by using an aqueous phase PVA solution; the capillary tube is tightly connected with a vertical main channel of the cross flow focusing type micro-fluidic device, and meanwhile, the oil phase solution is tightly connected with horizontal side channels on two sides of the cross flow focusing type micro-fluidic device through a hose; the inner diameter of the capillary tube is consistent with that of a vertical main channel of the cross flow focusing type micro-fluidic device;
controlling the flow rates of the vertical main channel and the horizontal side channels at two sides by using an injection pump, and adjusting the volume flow of the vertical main channel to be 30mL/h and the volume flow of the horizontal side channels to be 30 mL/h; forming a dispersed phase in the vertical main channel and forming a continuous phase in the horizontal side channels at two sides; when the dispersed phase and the continuous phase meet at a cross opening of the cross flow focusing type micro-fluidic device, the dispersed phase is sheared by the continuous phase to form solid-water-oil composite emulsion particles; after the solid-water-oil composite emulsion particles are formed, the solid-water-oil composite emulsion particles are conveyed through a lower-end straight pipeline of the cross flow focusing type micro-fluidic device to obtain the solid-water-oil composite emulsion particles.
The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is distributed in the range of 95-145 mu m, and the polydispersity index is 8%.
Example 4:
the preparation process of the oil phase solution comprises the following steps: taking the volume ratio of 2:1:1, uniformly stirring dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS, then adding 1-hexyl-3-methylimidazolium tetrafluoroborate and cyclopentasiloxane, stirring for 24 hours to obtain a mixed solution, and then adding the mixed solution into a high-voltage pulse processing chamber to process for 90 minutes by using a high-voltage pulse electric field; the parameters of the high-voltage pulse electric field treatment are as follows: the pulse amplitude is 12KV, the pulse frequency is 1200Hz, and the pulse width is 12 us; the dosage of the 1-hexyl-3-methylimidazolium tetrafluoroborate is 1 percent of the mass of the oil phase solution; the dosage of the cyclopentasiloxane is 1% of the mass of the oil phase solution. By improving the preparation method of the oil phase solution, the uniformity of the oil phase solution is improved, the thickness of the liquid film of the prepared solid-water-oil composite emulsion particle is further more uniform, and the polydispersity index is reduced.
The remaining process parameters and procedures were exactly the same as in example 3. The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is distributed in the range of 110-143 mu m, and the polydispersity index is 3%.
Example 5:
the preparation process of the oil phase solution comprises the following steps: taking the volume ratio of 2:1:1, uniformly stirring dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS, then adding 1-hexyl-3-methylimidazolium tetrafluoroborate and cyclopentasiloxane, stirring for 12 hours to obtain a mixed solution, and then adding the mixed solution into a high-voltage pulse processing chamber to process for 60 minutes by using a high-voltage pulse electric field; the parameters of the high-voltage pulse electric field treatment are as follows: the pulse amplitude is 15KV, the pulse frequency is 1000Hz, and the pulse width is 10 us; the dosage of the 1-hexyl-3-methylimidazolium tetrafluoroborate is 1.5 percent of the mass of the oil phase solution; the dosage of the cyclopentasiloxane is 0.5% of the mass of the oil phase solution.
The remaining process parameters and procedures were exactly the same as in example 3. The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is 115-145 mu m, and the polydispersity index is 3%.
Example 6:
in the first step, the obtained polystyrene hollow microspheres containing internal phase water are pretreated, and the process comprises the following steps: adding polystyrene hollow microspheres and hydrogen peroxide into a sealed container with a stirrer, soaking the polystyrene hollow microspheres in the hydrogen peroxide, introducing nitrogen into the container to saturate the feed liquid with nitrogen, and then placing the sealed container in an electron accelerator of 2.5MeV and 40mA for irradiation stirring treatment; the irradiation dose rate adopted by the irradiation is 200kGy/h, the irradiation dose is 400kGy, and the stirring speed is 200 r/min; the volume concentration of the hydrogen peroxide is 15%. The remaining process parameters and procedures were exactly the same as in example 3. The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is 112-147 mu m, and the polydispersity index is 4%.
Example 7:
in the first step, the obtained polystyrene hollow microspheres containing internal phase water are pretreated, and the process comprises the following steps: adding polystyrene hollow microspheres and hydrogen peroxide into a sealed container with a stirrer, soaking the polystyrene hollow microspheres in the hydrogen peroxide, introducing nitrogen into the container to saturate the feed liquid with nitrogen, and then placing the sealed container in an electron accelerator of 2.5MeV and 40mA for irradiation stirring treatment; the irradiation dose rate adopted by the irradiation is 200kGy/h, the irradiation dose is 400kGy, and the stirring speed is 200 r/min; the volume concentration of the hydrogen peroxide is 15%.
The remaining process parameters and procedures were exactly the same as in example 3. The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is distributed in the range of 118-148 mu m, and the polydispersity index is 3%.
Example 8:
in the first step, the obtained polystyrene hollow microspheres containing internal phase water are pretreated, and the process comprises the following steps: adding polystyrene hollow microspheres and hydrogen peroxide into a sealed container with a stirrer, soaking the polystyrene hollow microspheres in the hydrogen peroxide, introducing nitrogen into the container to saturate the feed liquid with nitrogen, and then placing the sealed container in an electron accelerator of 2.5MeV and 40mA for irradiation stirring treatment; the irradiation dose rate adopted by the irradiation is 200kGy/h, the irradiation dose is 400kGy, and the stirring speed is 200 r/min; the volume concentration of the hydrogen peroxide is 15%.
The remaining process parameters and procedures were exactly the same as in example 4. The result of geometric dimension test shows that the liquid film thickness of the obtained solid-water-oil composite emulsion particles is 130-150 mu m, and the polydispersity index is 2%.
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 (7)

1. A method for preparing monodisperse solid-water-oil composite emulsion particles, which is characterized by comprising the following steps:
preparing polystyrene hollow microspheres containing internal phase water, namely solid cores, by using a coaxial emulsion particle generator;
step two, preparing the cross flow focusing type micro-fluidic device with the controllable channel diameter by using a pouring method;
step three, preparing a water phase PVA solution and an oil phase solution with certain concentration according to the requirement of the density matching range;
step four, absorbing a plurality of polystyrene hollow microspheres containing internal phase water into a capillary by using an aqueous phase PVA solution; the capillary tube is tightly connected with a vertical main channel of the cross flow focusing type micro-fluidic device, and meanwhile, the oil phase solution is tightly connected with horizontal side channels on two sides of the cross flow focusing type micro-fluidic device through a hose;
controlling the flow rates of the vertical main channel and the horizontal side channels at two sides by using an injection pump, forming a dispersion phase in the vertical main channel and forming a continuous phase in the horizontal side channels at two sides; when the dispersed phase and the continuous phase meet at a cross opening of the cross flow focusing type micro-fluidic device, the dispersed phase is sheared by the continuous phase to form solid-water-oil composite emulsion particles; after the solid-water-oil composite emulsion particles are formed, the solid-water-oil composite emulsion particles are conveyed through a lower-end straight pipeline of the cross flow focusing type micro-fluidic device to obtain the solid-water-oil composite emulsion particles;
the molecular weight range of PVA in the PVA solution in the third step is 13000-146000; the hydrolysis degree range is 86-99 percent; the mass concentration range is 2-5%; the oil phase solution is a mixture of dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS;
the preparation process of the oil phase solution comprises the following steps: taking the volume ratio of 1-3: 1-3: 1-3 of dibutyl phthalate DBP, dioctyl phthalate DOP and sebacic acid diester DOS, uniformly stirring, adding 1-hexyl-3-methylimidazolium tetrafluoroborate and cyclopentasiloxane, stirring for 12-24 hours to obtain a mixed solution, and adding the mixed solution into a high-voltage pulse processing chamber to be processed for 60-90 min by using a high-voltage pulse electric field; the parameters of the high-voltage pulse electric field treatment are as follows: the pulse amplitude is 8-15 kV, the pulse frequency is 800-1200 Hz, and the pulse width is 8-12 mu s; the dosage of the 1-hexyl-3-methylimidazolium tetrafluoroborate is 0.5-1.5% of the mass of the oil phase solution; the dosage of the cyclopentasiloxane is 1-2% of the mass of the oil phase solution;
in the first step, the obtained polystyrene hollow microspheres containing internal phase water are pretreated, and the process comprises the following steps: adding polystyrene hollow microspheres and hydrogen peroxide into a sealed container with a stirrer, soaking the polystyrene hollow microspheres in the hydrogen peroxide, introducing nitrogen into the container to saturate the feed liquid with nitrogen, and then placing the sealed container in an electron accelerator of 2.5MeV and 40mA for irradiation stirring treatment; the irradiation dose rate adopted by irradiation is 100-200 kGy/h, the irradiation dose is 200-400 kGy, and the stirring speed is 100-200 r/min; the volume concentration of the hydrogen peroxide is 15-45%.
2. The method for preparing monodisperse solid-water-oil composite emulsion particles according to claim 1, wherein in the first step, the polystyrene hollow microspheres are replaced by any one of poly-alpha-methylstyrene, styrene-butadiene-styrene or polyacrylonitrile microspheres.
3. The method for preparing monodisperse solid-water-oil composite emulsion particles according to claim 1, wherein the polystyrene hollow microspheres in the first step have an inner diameter of 700-1300 μm and an inner diameter deviation of ± 10 μm.
4. The method for preparing monodisperse solid-water-oil composite emulsion particles according to claim 1, wherein the horizontal side channels at two sides of the cross flow focusing type microfluidic device in the second step are positioned on the same horizontal line, so that the horizontal side channels uniformly act on the disperse phase, thereby improving the monodispersity of the solid-water-oil composite emulsion particles; the diameter of the channel of the cross flow focusing type micro-fluidic device needs to ensure that the ratio of the solid core to the diameter of the pipeline is more than or equal to 0.65 and less than or equal to 0.85.
5. The method for preparing monodisperse solid-water-oil composite emulsion particle according to claim 1, wherein the density matching range in the third step is that the density difference between the solid core and the aqueous phase PVA solution is greater than or equal to-0.005 g/cm30.005g/cm or less3(ii) a Oil phase solution and water phase PVA solutionThe density matching range between the two is more than or equal to-0.008 g/cm3Less than or equal to 0.008g/cm3
6. The method for preparing monodisperse solid-water-oil composite emulsion particles according to claim 1, wherein the inner diameter of the capillary in the fourth step is consistent with the inner diameter of the vertical main channel of the cross flow focusing type microfluidic device.
7. The method for preparing monodisperse solid-water-oil composite emulsion particles according to claim 1, wherein in the fifth step, the flow rate ratio of the two horizontal side channels is greater than or equal to 0.8.
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