CN109092178A - A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil - Google Patents

A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil Download PDF

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Publication number
CN109092178A
CN109092178A CN201810800871.XA CN201810800871A CN109092178A CN 109092178 A CN109092178 A CN 109092178A CN 201810800871 A CN201810800871 A CN 201810800871A CN 109092178 A CN109092178 A CN 109092178A
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oil
water
phase
solid
milk particle
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CN109092178B (en
Inventor
潘大伟
陈强
刘梅芳
杨璨
李波
刘杨
刘一杨
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Laser Fusion Research Center China Academy of Engineering Physics
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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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Colloid Chemistry (AREA)

Abstract

The invention discloses it is a kind of prepare monodisperse it is solid-method of the compound milk particle of water-oil, this method is improved by using cross flow focusing shear mode consolidates the-monodispersity of the compound milk particle of water-oil;The concentration for adjusting oil-phase solution and PVA solution realizes the alternate density matching of solid-water-oil three to improve admittedly-water-oil compound milk particle yield;Adjust physical parameter (viscosity of oil-phase solution, oil water interfacial tension) and duty parameter (flow velocity of dispersed phase and continuous phase), monodispersed solid-compound milk particle of water-oil that thickness of liquid film range is 50 μm~150 μm has successfully been prepared in the thickness for controlling PVA liquid film layer.The channel diameter of generator can be changed according to the demand of targeted microspheres diameter by adjusting this method, easy to operate and applied widely.

Description

A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil
Technical field
The invention belongs to microfluidic controls for field of novel, and in particular to a kind of monodisperse for preparing consolidates-water-oil Composite Milk The method of grain.
Background technique
Due to the special construction (water phase as middle layer by solid core and outer separation of oil) of solid-compound milk particle of water-oil, It is widely used in microreactor, pharmaceuticals industry and the field laser inertial confinement fusion (ICF).In ICF Physical Experiment, Due to PVA to hydrogen have well resistance seep performance, polystyrene (PS)-polyvinyl alcohol (PVA) double-layer hollow microballoon and it is extensive As fuel container.Currently, the preparation of PS-PVA double-layer ball, which mainly passes through, solidifies solid-compound milk particle of water-oil.As it can be seen that solid- The monodispersity and thickness of liquid film of the compound milk particle of water-oil have important influence to the quality of PS-PVA double-layer hollow microballoon.
Currently, paddling process is widely used in the preparation of solid-compound milk particle of water-oil.This method is although easy to operate, but makes Standby obtained compound milk particle thickness of liquid film has wider distribution, and repeatability is low, and controllability is poor.Therefore, miniflow Control technology is developed the building for carrying out solid-compound milk particle of water-oil.Overseas utilization magnetive attraction pushes magnetic-particle to pass through oil-water interfaces To be consolidated-compound the milk particle of water-oil.The thickness of liquid film for solid-compound milk particle of water-oil that this method is prepared is very thin, and only Magnetic particle can be coated to limit its application field.Solid-water-is carried out using fluid driving particle in the prior art The building of the compound milk particle of oil.Early period successfully constructs solid-compound milk particle of water-oil using T-device.However since solid core exists It is not satisfactory (being greatly improved compared with paddling process) that the motor behavior of T-type mouth results in its monodispersity.Based on this, using ten Word flow focusing type micro fluidic device can effectively control solid core in the motor behavior of cross mouth.In addition, being flowed in cross In focus type micro fluidic device, continuous phase can provide uniform shear action.It can successfully be constructed using this method monodispersed Gu the compound milk particle of-water-oil.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later Point.
In order to realize these purposes and other advantages according to the present invention, provide it is a kind of prepare monodisperse it is solid-water-oil answers The method for closing milk particle, comprising the following steps:
Step 1: preparing the polystyrene hollow microballoon containing interior phase water, i.e. solid core using coaxial milk particle generator;
Step 2: preparing the controllable cross of channel diameter using casting flows focus type micro fluidic device;
Step 3: configuring certain density water phase PVA solution and oil-phase solution according to density matching area requirement;
Step 4: will be in several polystyrene hollow microballoon sucking capillaries containing interior phase water using water phase PVA solution;And The vertical main channel for making capillary flow focus type micro fluidic device with cross is closely connect, while utilizing hose by oil-phase solution It is closely connect with the horizontal by-pass in two sides of cross flowing focus type micro fluidic device;
Step 5: the flow velocity of vertical main channel Yu the horizontal by-pass in two sides is controlled using syringe pump, in vertical main channel Dispersed phase is formed, forms continuous phase in the horizontal by-pass in two sides;When dispersed phase and continuous phase flow focus type miniflow in cross When the cross mouth of control device meets, dispersed phase is sheared to form solid-compound milk particle of water-oil by continuous phase;Gu the compound milk particle of-water-oil After formation, conveyed by the lower end straight pipeline of cross flowing focus type micro fluidic device, consolidate-compound the milk particle of water-oil.
Preferably, polystyrene hollow microballoon replaces with poly alpha methylstyrene, styrene-fourth two in the step 1 Any one in alkene-styrene or polyacrylonitrile microballoon.
Preferably, the internal diameter of the polystyrene hollow microballoon in the step 1 is 700~1300 μm, and inner diameter deviation is ±10μm。
Preferably, the horizontal by-pass in two sides of the cross flowing focus type micro fluidic device in the step 2 is in same Make its stepless action in dispersed phase on one horizontal line, to improve the monodispersity of solid-compound milk particle of water-oil;The cross The channel diameter of flow focusing type micro fluidic device must guarantee that the ratio between solid core and pipe diameter are more than or equal to 0.65, be less than etc. In 0.85.
Preferably, the molecular weight ranges of PVA are 13000~146000 in the PVA solution in the step 3;Degree of hydrolysis Range is 86%~99%;Mass concentration range is 2%~5%;The oil-phase solution is dibutyl phthalate DBP, neighbour The mixture of phthalic acid dibutyl ester DOP and sebacic acid diester DOS.
Preferably, the process for preparation of the oil-phase solution are as follows: taking volume ratio is 1~3:1~3:1~3 O-phthalic Dibutyl phthalate DBP, o-phthalic acid dibutyl ester DOP and sebacic acid diester DOS are stirred evenly, and 1- hexyl -3- methyl is then added Imidazoles tetrafluoro boric acid and cyclopentasiloxane, stirring 12~for 24 hours, mixed solution is obtained, high-voltage pulse then is added in mixed solution 60~90min is handled using high-pressure pulse electric in process chamber;The parameter of high-pressure pulse electric processing are as follows: impulse amplitude is 8~15KV, pulse frequency are 800~1200Hz, and pulse width is 8~12us;1- hexyl -3- methylimidazole the tetrafluoro boric acid Dosage be oil-phase solution quality 0.5~1.5%;The dosage of the cyclopentasiloxane is the 1~2% of oil-phase solution quality.
Preferably, density of the density matching range in the step 3 between solid core and water phase PVA solution Poor range is more than or equal to -0.005g/cm3, it is less than or equal to 0.005g/cm3;Density between oil-phase solution and water phase PVA solution Matching range is more than or equal to -0.008g/cm3, it is less than or equal to 0.008g/cm3
Preferably, the vertical master of the internal diameter of capillary and cross flowing focus type micro fluidic device is logical in the step 4 The internal diameter in road is consistent.
Preferably, in the step 5, the velocity ratio of the horizontal by-pass in two sides is more than or equal to 0.8.
Preferably, in the step 1, the obtained polystyrene hollow microballoon containing interior phase water is pre-processed, Process are as follows: polystyrene hollow microballoon and hydrogen peroxide are added in the sealing container with stirring, soak polystyrene hollow microballoon Bubble is in hydrogen peroxide, and being passed through nitrogen thereto is saturated nitrogen in feed liquid, and the sealing container is then placed in 2.5MeV, 40mA Electron accelerator in carry out irradiation stir process;The radiation dose rate used that irradiates irradiates agent for 100~200kGy/h Amount is 200~400kGy, and mixing speed is 100~200r/min;The volumetric concentration of the hydrogen peroxide is 15~45%.
The present invention is include at least the following beneficial effects: the present invention by using cross flow focusing shear mode improve it is solid- The monodispersity of the compound milk particle of water-oil;Adjust oil mutually and the concentration of PVA solution realize solid-water-oil three-phase density matching thus Improve the yield of solid-compound milk particle of water-oil;Adjust physical parameter (viscosity of oil-phase solution, oil water interfacial tension) and operating condition ginseng Number (flow velocity of dispersed phase and continuous phase) controls the thickness of PVA liquid film layer, and it is 50 μm that thickness of liquid film range, which has successfully been prepared, ~150 μm of monodispersed solid-compound milk particle of water-oil.It is of the invention prepare monodisperse it is solid-method of the compound milk particle of water-oil can Change the channel diameter of generator according to the demand of targeted microspheres diameter, it is easy to operate and applied widely, it can effectively solve mesh Preceding paddling process method prepares solid-wide problem of the compound milk particle thickness of liquid film size distribution ranges of water-oil.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention:
Fig. 1 is the high speed that cross of the present invention flows the forming process of solid-compound milk particle of water-oil in focus type micro fluidic device Image photo;
Fig. 2 is the distribution map of the thickness of liquid film of solid-compound milk particle of water-oil obtained in the embodiment of the present invention 2.
Specific embodiment:
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more The presence or addition of a other elements or combinations thereof.
Embodiment 1:
A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil, comprising the following steps:
Step 1: preparing internal diameter using coaxial milk particle generator is 750 μm, the polyphenyl second containing interior phase water that wall thickness is 25 μm Alkene tiny balloon, i.e. solid core;
Step 2: preparing vertical main channel using casting and horizontal by-pass diameter is the cross flow focusing of 1mm Type micro fluidic device;
Step 3: configuring molecular weight according to density matching area requirement is 13000, degree of hydrolysis 86%, mass concentration is 2% PVA solution;Volume ratio is the oil-phase solution of the DBP and DOS of 144:66;
Step 4: will be in 50 polystyrene hollow microballoon sucking capillaries containing interior phase water using water phase PVA solution;And The vertical main channel for making capillary flow focus type micro fluidic device with cross is closely connect, while utilizing hose by oil-phase solution It is closely connect with the horizontal by-pass in two sides of cross flowing focus type micro fluidic device;
Step 5: controlling the flow velocity of vertical main channel Yu the horizontal by-pass in two sides using syringe pump, vertical main channel is adjusted Volume flow be 20mL/h, the volume flow of horizontal by-pass is 20mL/h;Dispersed phase is formed in vertical main channel, two Continuous phase is formed in the horizontal by-pass in side;When dispersed phase and continuous phase are in the cross mouth phase of cross flowing focus type micro fluidic device When chance, dispersed phase is sheared to form solid-compound milk particle of water-oil by continuous phase;Gu-water-oil Composite Milk particle shape is after, by cross The lower end straight pipeline of flow focusing type micro fluidic device conveys, consolidate-compound the milk particle of water-oil.
Geometric dimension test result shows that the thickness of liquid film of obtained solid-compound milk particle of water-oil is to be distributed in 95~135 μ Between m, polydispersity index 5%.
Embodiment 2:
A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil, comprising the following steps:
Step 1: preparing internal diameter using coaxial milk particle generator is 800 μm, the polyphenyl second containing interior phase water that wall thickness is 25 μm Alkene tiny balloon, i.e. solid core;
Step 2: preparing vertical main channel using casting and horizontal by-pass diameter is the cross flow focusing of 1mm Type micro fluidic device;
Step 3: configuring molecular weight according to density matching area requirement is 13000, degree of hydrolysis 86%, mass concentration is 2% PVA solution;Volume ratio is the oil-phase solution of the DBP and DOS of 2:1;
Step 4: will be in 50 polystyrene hollow microballoon sucking capillaries containing interior phase water using water phase PVA solution;And The vertical main channel for making capillary flow focus type micro fluidic device with cross is closely connect, while utilizing hose by oil-phase solution It is closely connect with the horizontal by-pass in two sides of cross flowing focus type micro fluidic device;
Step 5: controlling the flow velocity of vertical main channel Yu the horizontal by-pass in two sides using syringe pump, vertical main channel is adjusted Volume flow be 40mL/h, the volume flow of horizontal by-pass is 40mL/h;Dispersed phase is formed in vertical main channel, two Continuous phase is formed in the horizontal by-pass in side;When dispersed phase and continuous phase are in the cross mouth phase of cross flowing focus type micro fluidic device When chance, dispersed phase is sheared to form solid-compound milk particle of water-oil by continuous phase;Gu-water-oil Composite Milk particle shape is after, by cross The lower end straight pipeline of flow focusing type micro fluidic device conveys, consolidate-compound the milk particle of water-oil.
Geometric dimension test result shows that the thickness of liquid film of obtained solid-compound milk particle of water-oil is distributed in 85~125 μm Between, as shown in Fig. 2, polydispersity index 7%;Wherein, the calculation formula of polydispersity index are as follows:
δ=SD/dav
Wherein, SDFor the standard deviation of sample thickness of liquid film, davFor average thickness of liquid film;Assuming that a sample thickness of liquid film There is x1, x2, x3, xN, N number of numerical value, standard deviation calculation formula are as follows:
Embodiment 3:
A method of it preparing monodisperse and consolidates-compound the milk particle of water-oil, comprising the following steps:
Step 1: preparing internal diameter using coaxial milk particle generator is 850 μm, the polyphenyl second containing interior phase water that wall thickness is 25 μm Alkene tiny balloon, i.e. solid core;
Step 2: preparing vertical main channel using casting and horizontal by-pass diameter is the cross flow focusing of 1mm Type micro fluidic device;
Step 3: configuring molecular weight according to density matching area requirement is 15000, degree of hydrolysis 90%, mass concentration is 3% PVA solution;Volume ratio is the oil-phase solution of DBP, DOP and DOS of 2:1:1;
Step 4: will be in 50 polystyrene hollow microballoon sucking capillaries containing interior phase water using water phase PVA solution;And The vertical main channel for making capillary flow focus type micro fluidic device with cross is closely connect, while utilizing hose by oil-phase solution It is closely connect with the horizontal by-pass in two sides of cross flowing focus type micro fluidic device;The internal diameter and cross of the capillary flow The internal diameter of the vertical main channel of focus type micro fluidic device is consistent;
Step 5: controlling the flow velocity of vertical main channel Yu the horizontal by-pass in two sides using syringe pump, vertical main channel is adjusted Volume flow be 30mL/h, the volume flow of horizontal by-pass is 30mL/h;Dispersed phase is formed in vertical main channel, two Continuous phase is formed in the horizontal by-pass in side;When dispersed phase and continuous phase are in the cross mouth phase of cross flowing focus type micro fluidic device When chance, dispersed phase is sheared to form solid-compound milk particle of water-oil by continuous phase;Gu-water-oil Composite Milk particle shape is after, by cross The lower end straight pipeline of flow focusing type micro fluidic device conveys, consolidate-compound the milk particle of water-oil.
Geometric dimension test result shows that the thickness of liquid film of obtained solid-compound milk particle of water-oil is distributed in 95~145 μm, Polydispersity index 8%.
Embodiment 4:
The process for preparation of the oil-phase solution are as follows: take the dibutyl phthalate DBP, adjacent benzene two that volume ratio is 2:1:1 Formic acid dibutyl ester DOP and sebacic acid diester DOS are stirred evenly, and 1- hexyl -3- methylimidazole tetrafluoro boric acid and ring penta is then added Siloxanes, stirring for 24 hours, obtain mixed solution, and then mixed solution is added in high-voltage pulse process chamber and utilizes high-voltage pulse electric Field processing 90min;The parameter of the high-pressure pulse electric processing are as follows: impulse amplitude 12KV, pulse frequency 1200Hz, pulse Width is 12us;The dosage of the 1- hexyl -3- methylimidazole tetrafluoro boric acid is the 1% of oil-phase solution quality;Penta silicon of ring The dosage of oxygen alkane is the 1% of oil-phase solution quality.It is improved by the preparation method to oil-phase solution, improves the equal of oil-phase solution Even property further makes the thickness of liquid film of solid-compound milk particle of water-oil of preparation more uniform, reduces polydispersity index.
Remaining technological parameter and process with it is identical in embodiment 3.Geometric dimension test result is shown, is obtained Gu the thickness of liquid film of the compound milk particle of-water-oil is distributed in 110~143 μm, polydispersity index 3%.
Embodiment 5:
The process for preparation of the oil-phase solution are as follows: take the dibutyl phthalate DBP, adjacent benzene two that volume ratio is 2:1:1 Formic acid dibutyl ester DOP and sebacic acid diester DOS are stirred evenly, and 1- hexyl -3- methylimidazole tetrafluoro boric acid and ring penta is then added Siloxanes stirs 12h, obtains mixed solution, and then mixed solution is added in high-voltage pulse process chamber and utilizes high-voltage pulse electric Field processing 60min;The parameter of the high-pressure pulse electric processing are as follows: impulse amplitude 15KV, pulse frequency 1000Hz, pulse Width is 10us;The dosage of the 1- hexyl -3- methylimidazole tetrafluoro boric acid is the 1.5% of oil-phase solution quality;The ring penta The dosage of siloxanes is the 0.5% of oil-phase solution quality.
Remaining technological parameter and process with it is identical in embodiment 3.Geometric dimension test result is shown, is obtained Gu the thickness of liquid film of the compound milk particle of-water-oil is distributed in 115~145 μm, polydispersity index 3%.
Embodiment 6:
In the step 1, the obtained polystyrene hollow microballoon containing interior phase water is pre-processed, process are as follows: will Polystyrene hollow microballoon and hydrogen peroxide are added in the sealing container with stirring, and polystyrene hollow microballoon is made to be immersed in hydrogen peroxide In, and being passed through nitrogen thereto is saturated nitrogen in feed liquid, then accelerates the electronics that the sealing container is placed in 2.5MeV, 40mA Irradiation stir process is carried out in device;The radiation dose rate used that irradiates is 200kGy/h, irradiation dose 400kGy, stirring Speed is 200r/min;The volumetric concentration of the hydrogen peroxide is 15%.Remaining technological parameter and process with it is complete in embodiment 3 It is identical.Geometric dimension test result shows, the thickness of liquid film of obtained solid-compound milk particle of water-oil is distributed in 112~147 μm, more Monodispersity index 4%.
Embodiment 7:
In the step 1, the obtained polystyrene hollow microballoon containing interior phase water is pre-processed, process are as follows: will Polystyrene hollow microballoon and hydrogen peroxide are added in the sealing container with stirring, and polystyrene hollow microballoon is made to be immersed in hydrogen peroxide In, and being passed through nitrogen thereto is saturated nitrogen in feed liquid, then accelerates the electronics that the sealing container is placed in 2.5MeV, 40mA Irradiation stir process is carried out in device;The radiation dose rate used that irradiates is 200kGy/h, irradiation dose 400kGy, stirring Speed is 200r/min;The volumetric concentration of the hydrogen peroxide is 15%.
Remaining technological parameter and process with it is identical in embodiment 3.Geometric dimension test result is shown, is obtained Gu the thickness of liquid film of the compound milk particle of-water-oil is distributed in 118~148 μm, polydispersity index 3%.
Embodiment 8:
In the step 1, the obtained polystyrene hollow microballoon containing interior phase water is pre-processed, process are as follows: will Polystyrene hollow microballoon and hydrogen peroxide are added in the sealing container with stirring, and polystyrene hollow microballoon is made to be immersed in hydrogen peroxide In, and being passed through nitrogen thereto is saturated nitrogen in feed liquid, then accelerates the electronics that the sealing container is placed in 2.5MeV, 40mA Irradiation stir process is carried out in device;The radiation dose rate used that irradiates is 200kGy/h, irradiation dose 400kGy, stirring Speed is 200r/min;The volumetric concentration of the hydrogen peroxide is 15%.
Remaining technological parameter and process with it is identical in embodiment 4.Geometric dimension test result is shown, is obtained Gu the thickness of liquid film of the compound milk particle of-water-oil is distributed in 130~150 μm, polydispersity index 2%.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited In specific details and legend shown and described herein.

Claims (10)

1. it is a kind of prepare monodisperse it is solid-method of the compound milk particle of water-oil, which comprises the following steps:
Step 1: preparing the polystyrene hollow microballoon containing interior phase water, i.e. solid core using coaxial milk particle generator;
Step 2: preparing the controllable cross of channel diameter using casting flows focus type micro fluidic device;
Step 3: configuring certain density water phase PVA solution and oil-phase solution according to density matching area requirement;
Step 4: will be in several polystyrene hollow microballoon sucking capillaries containing interior phase water using water phase PVA solution;And make hair Tubule is closely connect with the vertical main channel of cross flowing focus type micro fluidic device, while utilizing hose by oil-phase solution and ten The horizontal by-pass in two sides of word flow focusing type micro fluidic device closely connects;
Step 5: controlling the flow velocity of vertical main channel Yu the horizontal by-pass in two sides using syringe pump, formed in vertical main channel Dispersed phase forms continuous phase in the horizontal by-pass in two sides;When dispersed phase and continuous phase flow the micro-fluidic dress of focus type in cross When the cross mouth set meets, dispersed phase is sheared to form solid-compound milk particle of water-oil by continuous phase;Gu-water-oil Composite Milk particle shape at After, it is conveyed by the lower end straight pipeline of cross flowing focus type micro fluidic device, consolidate-compound the milk particle of water-oil.
2. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 1 Middle polystyrene hollow microballoon replaces in poly alpha methylstyrene, s-B-S or polyacrylonitrile microballoon Any one.
3. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 1 In polystyrene hollow microballoon internal diameter be 700~1300 μm, inner diameter deviation be ± 10 μm.
4. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 2 In cross flowing focus type micro fluidic device the horizontal by-pass in two sides be in same horizontal line make its stepless action in Dispersed phase, to improve the monodispersity of solid-compound milk particle of water-oil;The channel of the cross flowing focus type micro fluidic device Diameter must guarantee that the ratio between solid core and pipe diameter are more than or equal to 0.65, be less than or equal to 0.85.
5. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 3 In PVA solution in PVA molecular weight ranges be 13000~146000;Degree of hydrolysis range is 86%~99%;Mass concentration model Enclose is 2%~5%;The oil-phase solution is dibutyl phthalate DBP, o-phthalic acid dibutyl ester DOP and sebacic acid two The mixture of ester DOS.
6. prepare as claimed in claim 5 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the oil mixes The process for preparation of liquid are as follows: taking volume ratio is 1~3:1~3:1~3 dibutyl phthalate DBP, o-phthalic acid dibutyl ester DOP and sebacic acid diester DOS are stirred evenly, and 1- hexyl -3- methylimidazole tetrafluoro boric acid and cyclopentasiloxane, stirring is then added 12~for 24 hours, mixed solution is obtained, then mixed solution is added in high-voltage pulse process chamber and utilizes high-pressure pulse electric processing 60 ~90min;The parameter of the high-pressure pulse electric processing are as follows: impulse amplitude is 8~15KV, and pulse frequency is 800~1200Hz, Pulse width is 8~12us;The dosage of the 1- hexyl -3- methylimidazole tetrafluoro boric acid be oil-phase solution quality 0.5~ 1.5%;The dosage of the cyclopentasiloxane is the 1~2% of oil-phase solution quality.
7. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 3 In density matching range be density contrast range between solid core and water phase PVA solution be more than or equal to -0.005g/cm3, Less than or equal to 0.005g/cm3;Density matching range between oil-phase solution and water phase PVA solution is more than or equal to -0.008g/ cm3, it is less than or equal to 0.008g/cm3
8. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 4 The internal diameter of middle capillary is consistent with the cross flowing internal diameter of vertical main channel of focus type micro fluidic device.
9. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step 5 In, the velocity ratio of the horizontal by-pass in two sides is more than or equal to 0.8.
10. prepare as described in claim 1 monodisperse it is solid-method of the compound milk particle of water-oil, which is characterized in that the step In one, the obtained polystyrene hollow microballoon containing interior phase water is pre-processed, process are as follows: by polystyrene hollow microballoon It is added in the sealing container with stirring with hydrogen peroxide, is immersed in polystyrene hollow microballoon in hydrogen peroxide, and be passed through thereto Nitrogen is saturated nitrogen in feed liquid, and then the sealing container is placed in the electron accelerator of 2.5MeV, 40mA irradiate and is stirred Mix processing;For the radiation dose rate used that irradiates for 100~200kGy/h, irradiation dose is 200~400kGy, mixing speed For 100~200r/min;The volumetric concentration of the hydrogen peroxide is 15~45%.
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CN113976052A (en) * 2021-11-03 2022-01-28 健进制药有限公司 Preparation system and preparation method of multivesicular liposome

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