CN109939621B - Method for preparing single-particle uniform coating shell layer by liquid phase interface crossing - Google Patents
Method for preparing single-particle uniform coating shell layer by liquid phase interface crossing Download PDFInfo
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Abstract
The invention provides a method for preparing a single-particle uniform coating shell layer by using liquid phase interface crossing. The method includes providing a shell phase, a continuous phase, and a core, the shell phase and the continuous phase being immiscible with each other; putting the shell phase and the continuous phase into the same container, and enabling the shell phase to be above the continuous phase; adding the core into the shell phase from the upper part of the shell phase, enabling the core to pass through the shell phase, so that the outer surface of the core is coated with a shell phase liquid film to form double-emulsified liquid drops, then immersing the double-emulsified liquid drops into the continuous phase, and enabling the double-emulsified liquid drops to flow along with the continuous phase to adjust the eccentricity of the core; and (3) curing the double-emulsion liquid drops subjected to eccentricity adjustment to solidify the shell phase liquid film to obtain the core-shell structure microsphere. The method is simple and convenient to operate, easy to realize and easy for industrial production, can effectively prepare the core-shell structure microspheres with uniform thickness and cores close to or positioned in a central area, and effectively utilizes a liquid phase interface to penetrate through and prepare a single-particle uniform coating shell layer.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method and a device for preparing a single-particle uniformly-coated shell layer by using liquid phase interface crossing, and a core-shell structure microsphere.
Background
In the related art, double emulsion droplets are a common research object in microfluidic technology and consist of an outer shell phase liquid membrane and an inner core. If a curable solution or reagent is used as the shell phase liquid film, the coated composite particle structure, namely the core-shell structure microsphere, can be prepared. Meanwhile, the core-shell structure microspheres prepared by the micro-fluidic method also have good monodispersity, so that the core-shell structure microspheres can meet the technical requirements of the application fields of chemical microreactors, drug delivery, catalytic carriers and the like. Therefore, the core-shell structure microspheres are widely applied to the subject fields of biology, chemistry, medicine, energy, environment and the like. However, in the core-shell structure microspheres prepared by using the conventional microfluidic double-emulsion droplet preparation device, the relative positions of the core and the shell in the core-shell structure microspheres are random, the thickness of the shell is often uneven, and the requirement on the uniformity of the core-shell structure microspheres is difficult to meet in application occasions.
Therefore, the existing related technology for preparing core-shell structure microspheres still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a method for preparing core-shell structure microspheres with uniform thickness and core close to or in the central region, which is simple, convenient, easy to implement, and easy for industrial production.
In one aspect of the invention, an apparatus for preparing core-shell structured microspheres is provided. According to an embodiment of the invention, the apparatus comprises: the device comprises a core coating pipeline, a first inlet is arranged at the top of the core coating pipeline, a first outlet is arranged at the bottom of the core coating pipeline, a shell phase and a continuous phase which are not mutually soluble are arranged in the core coating pipeline, the shell phase is arranged above the continuous phase, and the core coating pipeline is used for coating the outer surface of a core to form a shell phase liquid film so as to obtain double emulsified liquid drops, wherein the core enters the core coating pipeline from the first inlet and is output from the first outlet; a droplet rolling conduit having a second inlet in communication with the first outlet, a third inlet for inputting the continuous phase into the droplet rolling conduit, and a second outlet for providing a rolling region for the double emulsified droplets to adjust the eccentricity of the core; and a curing component, wherein the curing component is provided with a fourth inlet, the fourth inlet is communicated with the second outlet, and the curing component is used for curing the shell layer phase liquid film to form a shell layer (it is to be noted that the shell layer in the present invention, namely the aforementioned "single particle uniform coating shell layer", will not be described in detail hereinafter). The inventor finds that the device is simple in structure, convenient to operate and easy to realize industrialization, and can effectively prepare the core-shell structure microspheres with uniform thickness and cores close to or located in a central area.
According to an embodiment of the invention, the apparatus further comprises: a core feed assembly located above the first inlet for passing the core from the first inlet into the core cladding conduit.
According to an embodiment of the invention, the core clad pipe is arranged in a vertical direction.
According to an embodiment of the present invention, a length direction of the droplet rolling pipe is perpendicular to a length direction of the core cladding pipe.
According to an embodiment of the invention, the inner diameter of the droplet rolling conduit is not less than 2 times the diameter of the double emulsion droplets.
According to an embodiment of the invention, the apparatus further comprises: a continuous phase storage tank having a third outlet; a feed pump in communication with the continuous phase storage tank and the third inlet for delivering the continuous phase in the continuous phase storage tank to the droplet rolling conduit.
According to an embodiment of the invention, the curing assembly comprises: a shell curing conduit having a fifth inlet and a fourth outlet, the fifth inlet being in communication with the second outlet; and the solidifying device is arranged on the outer side of the shell layer solidifying pipeline and is used for solidifying the shell layer phase droplets.
According to an embodiment of the invention, the curing unit comprises at least one of an ultraviolet lamp and a heater.
According to the embodiment of the invention, the length direction of the shell solidification pipeline is consistent with the length direction of the liquid drop rolling pipeline.
According to an embodiment of the invention, the average density of the double emulsified droplets is different from the density of the continuous phase.
According to an embodiment of the invention, the core comprises at least one of zirconium dioxide and silicon dioxide; the shell phase comprises ethoxylated trimethylolpropane triacrylate; the continuous phase comprises a polyvinyl alcohol aqueous solution, wherein the mass fraction of the polyvinyl alcohol is 4.35-14.28%.
According to an embodiment of the present invention, the shell phase and/or the continuous phase further comprises a surfactant, and the mass fraction of the surfactant in the continuous phase or the shell phase is 0.1% to 2%.
According to the embodiment of the invention, the continuous phase further comprises a density regulator, and the mass fraction of the density regulator in the continuous phase is 5-30%.
In another aspect of the present invention, the present invention provides a method for preparing core-shell structure microspheres (it should be noted that the method for preparing core-shell structure microspheres herein is the aforementioned method for preparing a single-particle uniformly-coated shell layer by using liquid phase interface crossing, and will not be described in detail hereinafter). According to an embodiment of the invention, the method comprises: providing a shell phase, a continuous phase, and a core, wherein the shell phase is immiscible with the continuous phase; placing the shell phase and the continuous phase into the same container, and enabling the shell phase to be above the continuous phase; adding the core into the shell phase from the upper part of the shell phase, enabling the core to pass through the shell phase so that the outer surface of the core is coated with a shell phase liquid film to form double emulsified liquid drops, then immersing the double emulsified liquid drops into the continuous phase, and enabling the double emulsified liquid drops to flow with the continuous phase so as to adjust the eccentricity of the core; and curing the double emulsion droplets subjected to eccentricity adjustment to cure the shell phase liquid film to obtain the core-shell structure microsphere. The inventor finds that the method is simple and convenient to operate, easy to implement and easy for industrial production, and can effectively prepare the core-shell structure microspheres with uniform thickness and cores close to or positioned in the central area.
According to an embodiment of the invention, the flow velocity of the continuous phase is between 0.01m/s and 0.2 m/s.
In yet another aspect of the present invention, the present invention provides a core-shell structured microsphere. According to an embodiment of the present invention, the core-shell structured microsphere includes: a core; a shell layer covering the core, wherein the eccentricity of the core relative to the shell layer is not more than 20%. The inventor finds that the core-shell structure microsphere has uniform thickness, and the core is close to or positioned in the central area.
Drawings
Fig. 1 shows a schematic structural diagram of an apparatus for preparing core-shell structure microspheres according to an embodiment of the present invention.
Fig. 2 shows a schematic of the structure of a core in a droplet rolling conduit according to an embodiment of the invention.
Fig. 3 shows a schematic structural diagram of an apparatus for preparing core-shell structure microspheres according to another embodiment of the invention.
Fig. 4 shows a schematic structural diagram of an apparatus for preparing core-shell structure microspheres according to another embodiment of the present invention.
Fig. 5 shows a schematic structural diagram of an apparatus for preparing core-shell structure microspheres according to another embodiment of the invention.
Fig. 6 shows a schematic flow chart of a method for preparing core-shell structure microspheres according to an embodiment of the present invention.
Fig. 7 shows an optical microscope photograph of the core-shell structured microsphere according to an embodiment of the present invention.
FIG. 8 shows a scanning electron microscope photograph of core-shell structured microspheres according to an embodiment of the present invention.
Reference numerals:
h: inner diameter d of droplet rolling conduit: diameter of double emulsion droplets 1: double emulsion droplets 2: core-shell structure microspheres 10: apparatus for preparing core-shell structure microspheres 99: core 100: core clad pipe 110: first inlet 120: first outlet 130: shell phase 131: shell-phase liquid film 132: shell layer 140: continuous phase 200: droplet rolling conduit 210: second inlet 220: third inlet 230: second outlet 300: curing the assembly 310: fourth inlet 320: shell layer curing pipe 321: fifth inlet 322: fourth outlet 330: the curing device 400: core feed assembly 500: continuous phase storage tank 510: third outlet 600: feed pump
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, an apparatus for preparing core-shell structured microspheres is provided. According to an embodiment of the present invention, referring to fig. 1, the apparatus 10 for preparing core-shell structure microspheres includes: a core cladding pipe 100, wherein the core cladding pipe 100 is provided with a first inlet 110 at the top, a first outlet 120 at the bottom, and a shell phase 130 and a continuous phase 140 which are insoluble with each other are arranged inside, the shell phase 130 is positioned above the continuous phase 140, the core cladding pipe 100 is used for cladding a shell phase liquid film 131 on the outer surface of a core 99 so as to obtain a double emulsified liquid drop 1, wherein the core 99 enters the core cladding pipe 100 from the first inlet 110, and the core cladding pipe 100 is output from the first outlet 120; a rolling droplet conduit 200, said rolling droplet conduit 200 having a second inlet 210, a third inlet 220 and a second outlet 230, said second inlet 210 being in communication with said first outlet 120, said third inlet 220 for feeding said continuous phase 140 into said rolling droplet conduit 200, said rolling droplet conduit 200 for providing a rolling area for said double emulsified droplets 1 for adjusting the eccentricity of said core 99; and a curing assembly 300, the curing assembly 300 having a fourth inlet 310, the fourth inlet 310 being in communication with the second outlet 230, the curing assembly 300 being for curing the shell phase liquid film 131 to form the shell 132. The inventor finds that the device 10 for preparing the core-shell structure microspheres has a simple structure, is convenient to operate, is easy to realize industrialization, and can effectively prepare the core-shell structure microspheres 2 with uniform thickness and cores close to or positioned in a central area. According to the embodiment of the present invention, it should be noted that, in the structure shown in fig. 1, only the structures and the components of the apparatus 10 for preparing core-shell structure microspheres according to the present invention and the connection relationship between the structures and the components are shown, and the shape of each structure and the component is not to be understood as a limitation, and those skilled in the art can understand that the apparatus falls within the protection scope of the present invention as long as the above technical effects of the present invention can be achieved.
According to the embodiment of the present invention, a plurality of cores 99 are shown in fig. 1, and it should be noted that the plurality of cores 99 shown in fig. 1 can be understood as a schematic structural diagram of the apparatus 10 for preparing core-shell structure microspheres after a core 99 enters the core-shell structure pipeline 100 from the first inlet 110 at a predetermined time interval at the first inlet 110 of the core-shell structure pipeline 100 and after a plurality of cores 99 are present in the apparatus 10 for preparing core-shell structure microspheres; it can also be understood as a schematic representation of the position of the same core 99 in the apparatus 10 for preparing core-shell structured microspheres at predetermined time intervals, each interval being a short predetermined time. In summary, fig. 1 shows a schematic process diagram of the core 99 flowing in the apparatus 10 for preparing core-shell structure microspheres. Thus, as shown in fig. 1, in the apparatus 10 for preparing core-shell structure microspheres according to the present invention, the cores 99 can be coated one by one, thereby avoiding incomplete coating or excessive coating of the cores 99.
According to an embodiment of the present invention, referring to fig. 1, the apparatus provides a rolling region for the double emulsified liquid droplets 1 by using a liquid droplet rolling pipe 200, within the liquid droplet rolling region pipe 200, by continuously feeding the continuous phase 140 into the liquid droplet rolling pipe 200 from the third inlet 220, the poiseuille flow of the continuous phase 140 in the liquid droplet rolling pipe 200 drives the double emulsified liquid droplets 1 to roll adherently in the rolling region of the liquid droplet rolling pipe 200, during the rolling of the double emulsified liquid droplets 1, a shell phase liquid film 131 flows on the outer surface of the core 99 in a tangential direction (direction shown by arrow in fig. 1) along the outer surface of the core 99, a shell phase liquid film 131 flows on the outer surface of the core 99 at each point on the outer surface of the core 99 in a tangential direction along the outer surface of the core 99, generating a hydrodynamic pressure effect, the total force of the gravity and the buoyancy of the core 99 is balanced, so that the shell phase liquid film 131 is uniformly distributed on the outer surface of the core 99, the core 99 is close to or located in the central area of the double-emulsified liquid drop 1, and the core-shell structure microspheres 2 with uniform thickness and close to or located in the central area can be effectively prepared after the double-emulsified liquid drop 1 is solidified by the device 10 for preparing the core-shell structure microspheres.
According to an embodiment of the present invention, further, with reference to fig. 2, the inner diameter H of the droplet rolling conduit 200 is not less than 2 times the diameter d of the double emulsified droplets (it should be noted that in fig. 2, only a part of the droplet rolling conduit 200 is shown, and the continuous phase 140 in fig. 2 is only to indicate the role of the poisson flow of the continuous phase 140 in the apparatus of the present invention, and it will be understood by those skilled in the art that in a practical case, the double emulsified droplets having the core 99 and the shell phase liquid film 131 shown in fig. 2 are actually in the environment of the continuous phase 140). Thus, since the inner diameter H of the droplet rolling pipe 200 is not less than 2 times the diameter d of the double emulsion droplets, the poiseuille flow of the continuous phase 130 can better ensure that the double emulsion droplets roll adherently in the rolling area of the droplet rolling pipe 200, so that the shell phase liquid film 131 acts on the outer surface of the core 99 along the tangential direction of the outer surface of the core 99, and further the shell phase liquid film 131 at each point on the outer surface of the core 99 further flows along the tangential direction of the outer surface of the core 99, further generating hydrodynamic effect, and further balancing the resultant force of gravity and buoyancy of the core 99, so that the shell phase liquid film 131 is further uniformly distributed on the outer surface of the core 99, and the core 99 is close to or located in the central area of the double emulsion droplets, and then after the double emulsion droplets are solidified by the device for preparing the core-shell structure microspheres, the core-shell structure microspheres with uniform thickness and cores close to or positioned in the central area can be further effectively prepared.
According to an embodiment of the present invention, referring to fig. 1, the core clad pipe 100 is arranged in a vertical direction (it should be noted that, as will be understood by those skilled in the art, the vertical direction refers to a direction in which the core 99 receives gravity). Therefore, the gravity of the core 99 is utilized to coat the outer surface of the core 99 to form the shell phase liquid film 131, and the method is simple to operate, low in cost and easy to implement.
According to an embodiment of the present invention, referring to fig. 1, the length direction of the droplet rolling pipe 200 is perpendicular to the length direction of the core cladding pipe 100. Therefore, the double emulsified liquid drops 1 output from the first outlet 120 of the core-coated pipeline 200 and coated with the shell-phase liquid film 131 on the outer surface can smoothly enter the droplet rolling pipeline 200 from the second inlet 210, so that the poiseuille flow of the continuous phase 130 can better ensure that the double emulsified liquid drops 1 roll adherently in the rolling area of the droplet rolling pipeline 200, thus leading the shell-phase liquid film 131 to have the effect of flowing along the tangential direction of the outer surface of the core 99 on the outer surface of the core 99, leading the shell-phase liquid film 131 at each point on the outer surface of the core 99 to further have the effect of flowing along the tangential direction of the outer surface of the core 99, further generating hydrodynamic effect, further balancing the resultant force of gravity and buoyancy of the core 99, and leading the shell-phase liquid films 131 to be further uniformly distributed on the outer surface of the core 99, the core 99 is close to or located in the central area of the double-emulsified liquid drop 1, and then after the device 10 for preparing the core-shell structure microsphere solidifies the double-emulsified liquid drop 1, the core-shell structure microsphere 2 with uniform thickness and the core close to or located in the central area can be further effectively prepared.
According to the embodiments of the present invention, after a great deal of close examination and experimental verification of the relationship between the size of the core 99 and the thickness of the shell phase liquid film 131 coated on the outer surface of the core 99, the inventors found that the larger the size of the core 99 is, the larger the core 99 is, the core 99 is put into the shell phase 130, and the thicker the shell phase liquid film 131 coated on the outer surface of the core 99 is after it is put into the continuous phase 140 under the condition that the initial velocity of the core 99 and the initial height of the core from the liquid surface of the shell phase 130 are the same.
According to the embodiment of the present invention, after a great deal of intensive examination and experimental verification on the relationship between the initial velocity of the core 99, the initial height of the core 99 from the liquid level of the shell phase 130, and the thickness of the shell phase liquid film 131, the inventors found that, under the condition that the size of the core 99 is the same, the larger the initial velocity of the core 99 entering the shell phase 130 is, and the larger the height of the core 99 from the liquid level of the shell phase 130 is, the core 99 enters the shell phase 130, and after entering the continuous phase 140, the thicker the shell phase liquid film 131 is coated on the outer surface of the core 99.
According to an embodiment of the present invention, the average density of the double emulsified droplets 1 (note that the average density here refers to the ratio of the total mass of the double emulsified droplets to the volume of the double emulsified droplets) is different from the density of the continuous phase 140. Therefore, the double emulsified liquid drops 1 can smoothly enter the liquid drop rolling pipeline 200 from the core cladding pipeline 100, and the double emulsified liquid drops 1 are enabled to generate adherent rolling in the rolling area of the liquid drop rolling pipeline 200 through the Poisea flow of the continuous phase 130 in the liquid drop rolling pipeline 200, so that the shell phase liquid film 131 generates the action of flowing along the tangential direction of the outer surface of the core 99 on the outer surface of the core 99, and further the shell phase liquid film 131 of each point on the outer surface of the core 99 further generates the flowing along the tangential direction of the outer surface of the core 99, further generates the hydrodynamic pressure effect, and further balances with the resultant force of gravity and buoyancy of the core 99, so that the shell phase 131 is further uniformly distributed on the outer surface of the core 99, and the core 99 is enabled to be close to or positioned in the central area of the double emulsified liquid drops 1, and then after the double-emulsion liquid drop 1 is solidified by the device 10 for preparing the core-shell structure microsphere, the core-shell structure microsphere 2 with uniform thickness and a core close to or positioned in a central area can be further effectively prepared.
According to an embodiment of the present invention, the material of the core 99 may include zirconium dioxide, silicon dioxide, and the like. Therefore, a shell layer can be formed on the surface of the core 99 with a wide application range, and the prepared core-shell structure microsphere can meet the technical requirements of various application fields such as a chemical microreactor, drug delivery, a catalytic carrier and the like, and can be widely applied to the subject fields such as biology, chemistry, medicine, energy, environment and the like, so that the device has a wide application range and a wide commercial prospect.
According to an embodiment of the present invention, the shell phase 130 includes ethoxylated trimethylolpropane triacrylate, etc. Therefore, the core-shell structure microspheres can be well prepared, the prepared core-shell structure microspheres can meet the technical requirements of various application fields such as chemical microreactors, drug delivery and catalytic carriers, and can be widely applied to the subject fields such as biology, chemistry, medicine, energy, environment and the like, so that the device is wide in application range and wide in commercial prospect.
According to an embodiment of the present invention, the continuous phase 140 includes an aqueous solution of polyvinyl alcohol. In some embodiments of the present invention, in the aqueous solution of polyvinyl alcohol, the mass fraction of polyvinyl alcohol may be 4.35% to 14.28%, specifically, may be 4.35%, 9.32%, 14.28%, or the like. Therefore, the shell phase 130 and the continuous phase 140 are not mutually soluble, so that the double emulsion droplets 1 can better roll against each other in the rolling area of the droplet rolling pipeline 200 through the poiseuille flow of the continuous phase 130 in the droplet rolling pipeline 200, and thus the shell phase liquid film 131 acts on the outer surface of the core 99 along the tangential direction of the outer surface of the core 99, and further the shell phase liquid film 131 at each point on the outer surface of the core 99 further flows along the tangential direction of the outer surface of the core 99, further fluid dynamic pressure effect is generated, the resultant force of gravity and buoyancy of the core 99 is further balanced with each other, so that the shell phase liquid film 131 is further uniformly distributed on the outer surface of the core 99, and the core 99 is close to or located in the central area of the double emulsion droplets 1, and then after the double-emulsion liquid drop 1 is solidified by the device 10 for preparing the core-shell structure microsphere, the core-shell structure microsphere 2 with uniform thickness and a core close to or positioned in a central area can be further effectively prepared, and the device has the advantages of wide and easily-obtained material source and lower cost.
In other embodiments of the present invention, the shell phase 130 and/or the continuous phase 140 further include a surfactant, the mass fraction of the surfactant in the continuous phase 140 or the shell phase 130 is 0.1% to 2%, the kind of the surfactant is not particularly limited, and those skilled in the art can flexibly select the surfactant according to needs. Therefore, the surface tension of the shell phase 130 and/or the continuous phase 140 can be reduced, so that the double emulsion droplets can better pass through the interface between the shell phase 130 and the continuous phase 140, the shell phase liquid film 131 is completely coated on the outer surface of the core 99, and the shell phase liquid film 131 is further uniformly distributed on the outer surface of the core 99, so that the core 99 is close to or located in the central region of the double emulsion droplet 1, and further, after the device 10 for preparing core-shell structure microspheres solidifies the double emulsion droplet 1, the core-shell structure microspheres 2 with uniform thickness and cores close to or located in the central region can be further effectively prepared.
In other embodiments of the present invention, the continuous phase 140 may further include a density modifier, and the mass fraction of the density modifier in the continuous phase may be 5% to 30%. In some embodiments of the invention, the density modifier may be a heavy salt, such as sodium tungstate or the like. Therefore, the density of the continuous phase 140 can be adjusted to be appropriate, and the double emulsified liquid drops 1 can be better caused to roll adherently in the rolling area of the liquid drop rolling pipeline 200 through the poiseuille flow of the continuous phase 130 in the liquid drop rolling pipeline 200, so that the shell phase liquid film 131 acts on the outer surface of the core 99 along the tangential direction of the outer surface of the core 99, further the shell phase liquid film 131 at each point on the outer surface of the core 99 further flows along the tangential direction of the outer surface of the core 99, further a hydrodynamic effect is generated, the resultant force of gravity and buoyancy of the core 99 is further balanced with each other, and the shell phase liquid film 131 is further uniformly distributed on the outer surface of the core 99, so that the core 99 is close to or positioned in the central area of the double emulsified liquid drops 1, and then after the double-emulsion liquid drop 1 is solidified by the device 10 for preparing the core-shell structure microsphere, the core-shell structure microsphere 2 with uniform thickness and a core close to or positioned in a central area can be further effectively prepared.
According to an embodiment of the present invention, referring to fig. 3, the apparatus further comprises: a core dosing assembly 400, the core dosing assembly 400 being located above the first inlet 120 for the core 99 to enter the core cladding conduit 100 from the first inlet 110. In some embodiments of the invention, the core feed assembly 400 may be a motorized lift platform. Therefore, the device has simple structure, easy use and easy industrialization.
According to an embodiment of the present invention, referring to fig. 4, the apparatus further includes: a continuous phase storage tank 500, the continuous phase storage tank 500 having a third outlet 510; a feed pump 600, the feed pump 600 communicating with the continuous phase storage tank 500 and the third inlet 220 for feeding the continuous phase 130 in the continuous phase storage tank 500 into the droplet rolling conduit 200. It should be noted that the continuous phase storage vessel 500 is to be understood broadly herein, i.e., any vessel that can store the continuous phase, such as a syringe, etc.; in addition, the feed pump 600 may be a digitally controlled flow pump or the like. Therefore, the device has simple structure, easy use and easy industrialization.
Referring to fig. 5, the curing assembly 300 includes, according to an embodiment of the present invention: shell curing duct 320, said shell curing duct 320 having a fifth inlet 321 and a fourth outlet 322, said fifth inlet 321 being in communication with said second outlet 230 (it should be noted that, when said double emulsion droplet 1 enters said shell curing duct 320 from said fifth inlet 321, the "fifth inlet 321" of shell curing duct 320 and the "fourth inlet 310" of curing assembly 300 may be the same structure); a solidifier 330, wherein the solidifier 330 is arranged outside the shell phase solidification pipeline 320 and is used for solidifying the shell phase liquid drop 131. In some embodiments of the present invention, the length direction of the shell solidification pipe 320 coincides with the length direction of the droplet rolling pipe 200. Therefore, the double emulsified liquid drops 1 are easy to roll in a rolling area of the liquid drop rolling pipeline 200, so that the shell phase liquid film 131 flows on the outer surface of the core 99 along the tangential direction of the outer surface of the core 99, the shell phase liquid film 131 at each point on the outer surface of the core 99 further flows along the tangential direction of the outer surface of the core 99, a hydrodynamic effect is further generated, the hydrodynamic effect is further balanced with the resultant force of the gravity and the buoyancy of the core 99, the shell phase liquid film 131 is further uniformly distributed on the outer surface of the core 99, the core 99 is close to or positioned in the central area of the double emulsified liquid drops 1, and the double emulsified liquid drops 1 are further effectively prepared and have uniform thickness after the device 10 for preparing microspheres with core-shell structure solidifies the double emulsified liquid drops 1, The core is close to or positioned in the core-shell structure microsphere 2 of the central area.
According to an embodiment of the present invention, the curing unit includes at least one of an ultraviolet lamp and a heater, and different kinds of curing units correspond to different curing modes. Therefore, the curing mode of the invention can be light curing or heat curing, when the curing is light curing, a photoinitiator is required to be added into the shell phase, and the volume fraction of the photoinitiator can be 1-5%. Therefore, the method is simple and convenient to operate, easy to realize and easy to realize industrial production.
In another aspect of the present invention, the present invention provides a method for preparing a core-shell structured microsphere. According to an embodiment of the invention, referring to fig. 6, the method comprises the steps of:
s100: providing a shell phase, a continuous phase, and a core, wherein the shell phase is immiscible with the continuous phase.
According to the embodiment of the present invention, the materials of the shell phase, the continuous phase, the core, and the like are the same as those described above, and thus redundant description is omitted.
S200: and putting the shell phase and the continuous phase into the same container, and enabling the shell phase to be above the continuous phase.
S300: adding the core into the shell phase from the upper part of the shell phase, enabling the core to pass through the shell phase, so that the outer surface of the core is coated with a shell phase liquid film to form double emulsified liquid drops, then immersing the double emulsified liquid drops into the continuous phase, and enabling the double emulsified liquid drops to flow along with the continuous phase so as to adjust the eccentricity of the core.
According to an embodiment of the invention, the flow velocity of the continuous phase is between 0.01m/s and 0.2 m/s. Therefore, the flow velocity of the continuous phase is proper, at the flow velocity, the thickness of a shell phase liquid film coated on the outer surface of a core can be controlled, in the droplet rolling area pipeline, the continuous phase is continuously input into the droplet rolling pipeline from the third inlet, the double emulsified droplets are driven to generate adherent rolling in the rolling area of the droplet rolling pipeline by the Poisson flow of the continuous phase in the droplet rolling pipeline, in the process of rolling the double emulsified droplets, the shell phase liquid film generates flow on the outer surface of the core along the tangential direction of the outer surface of the core, the shell phase liquid film at each point on the outer surface of the core generates flow along the tangential direction of the outer surface of the core, a hydrodynamic pressure effect is generated, and the resultant force of gravity and buoyancy of the core is balanced with each other, therefore, the shell phase liquid film is uniformly distributed on the outer surface of the core, the core is close to or positioned in the central area of the double-emulsion liquid drop, and the core-shell structure microsphere with uniform thickness and close to or positioned in the central area can be effectively prepared after the double-emulsion liquid drop is solidified by the device for preparing the core-shell structure microsphere.
S400: and curing the double emulsion droplets subjected to eccentricity adjustment to cure the shell phase liquid film to obtain the core-shell structure microsphere.
According to the embodiment of the present invention, the device and the method of the curing treatment are the same as those described above, and will not be described in detail herein.
According to the embodiment of the invention, after the core-shell structure microspheres are obtained, cleaning treatment can be performed on the core-shell structure microspheres, and the cleaning treatment step can be a conventional cleaning treatment step and is not described in detail herein.
According to the embodiment of the present invention, the method of the present invention can be performed by using the apparatus described above, and the specific operation manner is the same as that described above, and will not be described herein again.
In yet another aspect of the present invention, the present invention provides a core-shell structured microsphere. According to an embodiment of the present invention, the core-shell structured microsphere includes: a core; a shell layer covering the core, wherein the eccentricity of the core relative to the shell layer is not more than 20%. The inventor finds that the core-shell structure microsphere has uniform thickness, and the core is close to or positioned in the central area.
According to the embodiment of the present invention, the materials for forming the core-shell structure microspheres are the same as those described above, and therefore, redundant description is omitted.
The following describes embodiments of the present invention in detail.
Example 1
Preparing an aqueous solution of ETPTA (ethoxylated trimethylolpropane triacrylate), PVA (polyvinyl alcohol) and sodium tungstate containing a photoinitiator, and ZrO2The ceramic microspheres are respectively used as a shell phase, a continuous phase and a core. Wherein, the volume ratio of the photoinitiator in the shell phase to the ETPTA reagent is 3 percent; PVA grains and sodium tungstate in the continuous phase respectively account for 10 percent and 20 percent of deionized water by mass. The continuous phase solution was filled in a 10mL syringe and connected to the second inlet 220 of the droplet rolling tube shown in fig. 5 (refer to fig. 5), and the syringe was loaded on the digital control flow pump.
Sealing the fourth outlet 322 shown in FIG. 5, injecting the continuous phase from the second inlet 220 to raise the liquid level in the core-coating tube to a height of 10-30cm, and carefully dropping a shell phase on the liquid level with a dropper, thenThen ZrO is mixed2The ceramic microspheres are thrown off from the upper part of the container one by one, and ZrO2When the ceramic microspheres pass through the shell phase and enter the continuous phase, double emulsified liquid drops are formed, then the double emulsified liquid drops continuously fall into the liquid drop rolling pipeline, and when the double emulsified liquid drops form stable rolling motion in the liquid drop rolling pipeline, the shell curing pipeline is irradiated by an ultraviolet lamp, so that the double emulsified liquid drops are irradiated by ultraviolet light for not less than 2 seconds in the rolling process, and the shell phase can be fully cured. And then collecting the solidified particles by using a culture dish containing the continuous phase solution to obtain the core-shell structure microspheres.
Transferring the core-shell structure microspheres into a glass bottle by using a pipettor, and cleaning the core-shell structure microspheres by using deionized water, wherein the specific method comprises the following steps: after adding deionized water, the glass bottle is placed on a shaker, and is cleaned by adjusting the speed to 140r/min for 5 times, each time, the water is changed for cleaning for 15 minutes, and then the glass bottle is dried for 24 hours at room temperature.
An optical microscope photograph of the core-shell structure microsphere prepared by the above process steps is shown in fig. 7, the prepared core-shell structure microsphere is embedded into resin, and is polished by sand paper, then the polished surface is cleaned and dried by deionized water, the eccentricity condition of the core in the core-shell structure microsphere can be observed under a scanning electron microscope (as shown in fig. 8), and the eccentricity ratio is counted (a statistical method of the eccentricity ratio: a calculation formula of the eccentricity ratio is shown in the specification)
Wherein e is the distance (m) between the core and the core of the core-shell structure microsphere, RSRadius (m), R of core-shell structure microsphereCRadius of the core (m); respectively counting e and R of each core-shell structure microsphere by using image processing softwareS、RCAnd then substituting the formula to calculate the eccentricity ratio of the core-shell ceramic microspheres), and obtaining the core-shell ceramic microspheres with 80% of particles, wherein the eccentricity ratio is less than 0.2 (the density difference between the core and the shell is 5 times).
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. An apparatus for preparing core-shell structure microspheres, comprising:
the device comprises a core coating pipeline, a first inlet is arranged at the top of the core coating pipeline, a first outlet is arranged at the bottom of the core coating pipeline, a shell phase and a continuous phase which are not mutually soluble are arranged in the core coating pipeline, the shell phase is arranged above the continuous phase, and the core coating pipeline is used for coating the outer surface of a core to form a shell phase liquid film so as to obtain double emulsified liquid drops, wherein the core enters the core coating pipeline from the first inlet and is output from the first outlet;
a droplet rolling conduit having a second inlet in communication with the first outlet, a third inlet for inputting the continuous phase into the droplet rolling conduit, and a second outlet for providing a rolling region for the double emulsified droplets to adjust the eccentricity of the core; and
a curing assembly having a fourth inlet in communication with the second outlet, the curing assembly for curing the shell phase liquid film to form a shell.
2. The apparatus of claim 1, further comprising:
a core feed assembly located above the first inlet for passing the core from the first inlet into the core cladding conduit.
3. The apparatus of claim 1, wherein the core clad conduit is disposed in a vertical orientation,
optionally, the length direction of the droplet rolling conduit is perpendicular to the length direction of the core cladding conduit.
4. The apparatus of claim 1, wherein the inner diameter of the droplet rolling conduit is no less than 2 times the diameter of the double emulsion droplets.
5. The apparatus of claim 1, further comprising:
a continuous phase storage tank having a third outlet;
a feed pump in communication with the continuous phase storage tank and the third inlet for delivering the continuous phase in the continuous phase storage tank to the droplet rolling conduit.
6. The apparatus of claim 1, wherein the curing assembly comprises:
a shell curing conduit having a fifth inlet and a fourth outlet, the fifth inlet being in communication with the second outlet;
a solidifier arranged outside the shell layer solidifying pipeline and used for solidifying the shell layer phase droplets,
optionally, the curing apparatus includes at least one of an ultraviolet lamp and a heater,
optionally, the length direction of the shell solidification pipeline is consistent with the length direction of the droplet rolling pipeline.
7. The device of claim 1, wherein the double emulsion droplets have an average density that is different from the density of the continuous phase,
optionally, the core comprises at least one of zirconia and silica; the shell phase comprises ethoxylated trimethylolpropane triacrylate; the continuous phase comprises a polyvinyl alcohol aqueous solution, wherein the mass fraction of polyvinyl alcohol is 4.35-14.28%;
optionally, the shell phase and/or the continuous phase further comprises a surfactant, and the mass fraction of the surfactant in the continuous phase or the shell phase is 0.1-2%;
optionally, the continuous phase further comprises a density regulator, and the mass fraction of the density regulator in the continuous phase is 5-30%.
8. A method for preparing microspheres with a core-shell structure is characterized by comprising the following steps:
providing a shell phase, a continuous phase, and a core, wherein the shell phase is immiscible with the continuous phase;
placing the shell phase and the continuous phase into the same container, and enabling the shell phase to be above the continuous phase;
adding the core into the shell phase from the upper part of the shell phase, enabling the core to pass through the shell phase so that the outer surface of the core is coated with a shell phase liquid film to form double emulsified liquid drops, then immersing the double emulsified liquid drops into the continuous phase, and enabling the double emulsified liquid drops to flow with the continuous phase so as to adjust the eccentricity of the core;
and curing the double emulsion droplets subjected to eccentricity adjustment to cure the shell phase liquid film to obtain the core-shell structure microsphere.
9. The method of claim 8, wherein the flow velocity of the continuous phase is 0.01m/s to 0.2 m/s.
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| CN117460572A (en) * | 2021-06-11 | 2024-01-26 | 国立大学法人鹿儿岛大学 | Capsule manufacturing method and capsule manufacturing apparatus |
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