CN110605075A - Janus microsphere and preparation method thereof - Google Patents

Janus microsphere and preparation method thereof Download PDF

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Publication number
CN110605075A
CN110605075A CN201910482577.3A CN201910482577A CN110605075A CN 110605075 A CN110605075 A CN 110605075A CN 201910482577 A CN201910482577 A CN 201910482577A CN 110605075 A CN110605075 A CN 110605075A
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microspheres
water
janus
concentration
polymer
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刘善芹
胡林峰
张毅军
张万庆
刘鹏飞
吴玉会
安金丽
李娟�
徐鹤
许坤
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Henan Institute of Science and Technology
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Henan Institute of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons

Abstract

The invention discloses a Janus microsphere and a preparation method thereof, the Janus microsphere can be prepared by only one homopolymer, and the limitation of preparing the Janus microsphere by different substances in the past is broken through. The preparation method of the Janus microspheres comprises the steps of taking polymers dissolved by organic solvents with density smaller than that of water and cosurfactants as oil phases, taking ultrapure water as water phases, mixing and shaking the oil phases and the water phases uniformly to prepare emulsion droplets, placing the emulsion droplets in a volatilization device, standing for 1-24 hours at room temperature, sucking precipitates, collecting the precipitates into a centrifugal tube, standing for 24 hours, washing the precipitates, removing supernatant, adding ultrapure water into the precipitates, washing and standing for 24 hours to obtain the Janus microspheres.

Description

Janus microsphere and preparation method thereof
Technical Field
The invention relates to a preparation technology of Janus microspheres, in particular to Janus microspheres and a preparation method thereof.
Background
In recent years, polymer microspheres have been widely used in drug carriers, catalysts, immunobiology and the like, have received more and more attention, and are widely used in the fields of biology, physics, chemistry and medicine. In 1991, de Gennes first proposed definition of Janus to represent particles with different structures and chemical properties on the surface, and anisotropic Janus nanomaterials became a research hotspot in the field of materials. Janus particles are nano particles with asymmetric structures which are gradually developed in recent years, and attract more interests of domestic and foreign scientists due to the asymmetric characteristics of the structure and the performance of the nano particles.
With the exploration of researchers on Janus nano particles, the Janus nano particles can be greatly changed in composition and form, so that the material is gradually developed in the aspects of theoretical research and application research in various fields, and has good application prospects in the aspects of biological carriers, emulsion stability, optics, biosensing, catalysts and the like. The Janus structure microsphere has unique dual properties due to the asymmetric chemical structure, not only retains the advantages and characteristics of the nano-scale material, but also shows great potential in the aspect of anisotropy. However, since Janus microspheres are small in size and difficult to control, it is a great difficulty in the field of polymer materials to develop a simple and effective preparation method.
At present, great progress has been made in preparation of Janus microspheres, and many methods have been researched to prepare asymmetric Janus structure polymer microspheres, such as a microfluidic method, a Pickering emulsion method, a phase separation method, a self-assembly method, an emulsion-solvent volatilization method and the like, which can effectively prepare Janus microspheres. However, these methods except the phase separation method are not suitable for large-scale production, and the phase separation method itself has a certain limitation, so that the preparation of the Janus microspheres is still in an experimental stage at present. How to simply and effectively prepare an asymmetric Janus structure polymer with uniform size and novel structure and find out the universality thereof is a challenging task in the field of material science at present.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides Janus microspheres and a preparation method thereof.
The technical scheme of the invention is as follows: a preparation method of Janus microspheres uses an organic solvent with density less than that of water to dissolve a polymer and a cosurfactant as oil phases; dissolving a surfactant as a water phase by using ultrapure water; mixing the oil phase and the water phase, shaking uniformly to prepare emulsion liquid drops, placing the emulsion liquid drops in a volatilization device, standing for 1-24 hours at room temperature, sucking the precipitate by using a rubber-head dropper after the organic solvent is completely volatilized, collecting the precipitate in a centrifugal tube, standing for 24 hours, washing the precipitate, sucking supernatant liquid by using the rubber-head dropper, adding ultrapure water for washing, and standing for 24 hours to obtain the emulsion.
Further improvements of the invention include:
the organic solvent is mainly toluene, the cosurfactant is n-hexadecanol, the polymer is polystyrene, and the surfactant is sodium dodecyl sulfate.
The volume ratio of the oil phase to the water phase is 1:10, the concentration of the polymer in the oil phase is generally 10mg/mL, the concentration of n-hexadecanol is generally less than 3mg/mL, and the concentration of the water phase is generally 3 mg/mL.
The emulsion droplets are placed 0.5-1.5mm below the liquid level of the water in the volatilization device.
The roughness of the Janus microspheres is adjusted by adjusting the concentration of organic solvent, polymer, co-surfactant, and the height of the emulsion droplets in water.
Another object of the present invention is to provide Janus microspheres prepared by the above method.
The preparation method adopts an emulsion-solvent volatilization method and utilizes the phenomenon of interface instability to prepare the asymmetric Janus structure polymer microspheres with controllable roughness. Emulsion liquid drops are prepared by an organic solution of a ternary system of Polystyrene (PS), normal hexadecanol (CA) and toluene and a Sodium Dodecyl Sulfate (SDS) aqueous solution through a shaking method, an organic solvent is volatilized at room temperature to obtain the asymmetric Janus structure microspheres with rough surfaces, the SDS has the function of reducing the interfacial tension, the surface morphology of the microspheres is fixed, the cosurfactant further reduces the surface tension, the phenomenon of interface instability is induced to occur, the interfacial tension of the microspheres is reduced to zero or an instantaneous negative value, and the surfaces of the microspheres are uneven and rough. The density of the organic solvent toluene is less than that of water, when the organic solvent toluene volatilizes in a volatilization device, one part of the microspheres is embedded below the liquid level, the other part of the microspheres is exposed in the air, after the toluene volatilizes completely, the surface of the part below the liquid level of the polymer microspheres becomes rough, but the other part of the polymer microspheres exposed in the air is unchanged and still has a smooth surface, and therefore the Janus microspheres which are rough in part and smooth in part are prepared. The invention also researches the influence of SDS concentration, CA concentration, PS concentration, water layer height, cosolvent (ethanol, acetone, tetrahydrofuran) ratio and the like on the roughness of the microspheres and the ratio of the intercalation liquid level.
Drawings
FIG. 1a is a scanning electron micrograph of asymmetric Janus microspheres obtained by changing the concentration of PS to 10 mg/mL.
FIG. 1b is a scanning electron micrograph of asymmetric Janus microspheres obtained by changing the concentration of PS to 15 mg/mL.
FIG. 1c is a scanning electron micrograph of asymmetric Janus microspheres obtained by changing the concentration of PS to 20 mg/mL.
FIG. 2a is a scanning electron micrograph of polymer microspheres obtained by changing the concentration of CA in emulsion droplets to 0.1 mg/mL.
FIG. 2b is a scanning electron micrograph of the polymeric microspheres obtained by varying the concentration of CA in the emulsion droplets to 0.5 mg/mL.
FIG. 2c is a scanning electron micrograph of polymeric microspheres obtained by varying the CA concentration in the emulsion droplets to 3.0 mg/mL.
FIG. 3a is a scanning electron microscope image of the asymmetric Janus structure polymer microsphere obtained by regulating and controlling the height of the water layer to 0.5 mm.
FIG. 3b is a scanning electron microscope image of the asymmetric Janus structure polymer microsphere obtained by regulating and controlling the height of the water layer to 0.7 mm.
FIG. 3c is a scanning electron microscope image of the asymmetric Janus structure polymer microsphere obtained by regulating and controlling the height of the water layer to 1.3 mm.
FIG. 4a shows that the volume ratio of toluene to acetone is controlled to be 1: 2, and 2, obtaining a scanning electron microscope image of the asymmetric Janus structure polymer microsphere.
FIG. 4b shows the volume ratio of toluene to acetone is controlled to be 1:1, and 1, obtaining a scanning electron microscope image of the asymmetric Janus structure polymer microsphere.
Fig. 4c regulates the volume ratio of toluene to acetone to be 5: 1, and 1, obtaining a scanning electron microscope image of the asymmetric Janus structure polymer microsphere.
FIG. 5a is a scanning electron microscope image of the asymmetric Janus structure polymer microsphere obtained by regulating the volume ratio of toluene to ethanol to be 2: 3.
FIG. 5b is a graph showing the volume ratio of toluene to ethanol adjusted to 3: 2, and 2, obtaining a scanning electron microscope image of the asymmetric Janus structure polymer microsphere.
FIG. 6a is a scanning electron micrograph of a product prepared in example 6 at a SDS concentration of 3mg/mL, a PS concentration of 10mg/mL, and a CA concentration of 0.6 mg/mL.
FIG. 6b is a scanning electron micrograph of a product prepared in example 6 at a SDS concentration of 3mg/mL, a PS concentration of 10mg/mL, and a CA concentration of 1.3 mg/mL.
FIG. 6c is a scanning electron micrograph of a product prepared in example 6 at a SDS concentration of 3mg/mL, a PS concentration of 10mg/mL, and a CA concentration of 2.1 mg/mL.
Detailed Description
Example 1
Preparation of asymmetric Janus structure polymer microsphere
The invention uses emulsion-solvent volatilization method, that is, polymer is dissolved in organic solvent which is not compatible with water, then the solution and water phase are emulsified, and the polymer is solidified to form microspheres with various shapes along with the volatilization of the organic solvent in emulsion droplets. In addition, emulsion droplets were prepared by hand shaking. The oil phase is organic solvent toluene dissolved Polystyrene (PS) and n-hexadecanol (CA), the concentration of PS is 10mg/mL, and the concentration of CA is generally less than 3 mg/mL. Sodium Dodecyl Sulfate (SDS) was dissolved in ultrapure water to prepare an aqueous phase, and the concentration was generally 3 mg/mL. Injecting 1mL of water phase into a 5mL reagent bottle with a cover, injecting 100 mu L of oil phase below the liquid surface, screwing the bottle cover, and manually shaking for 3-5 times to prepare emulsion droplets. Immediately, 100. mu.L of the emulsion was placed in a volatilization device having a water layer of different heights, and observed under an optical microscope. Standing for 1-24 hours at room temperature, sucking a small amount of precipitate by using a rubber-head dropper after toluene is completely volatilized, collecting the precipitate in a centrifugal tube, standing for 24 hours, washing the precipitate, sucking supernatant liquid by using the rubber-head dropper, adding ultrapure water for washing, standing for 24 hours, repeating for 1-2 times, and then carrying out sample preparation and characterization.
In the volatilization device, the organic solvent toluene gradually volatilizes, SDS and CA are adsorbed on an oil/water interface layer, and then the surface of emulsion liquid drops shrinks, the area of the interface is reduced, and the phenomenon of interface instability occurs. The volatilization rate of toluene can be controlled by changing the height of the water layer, and the higher the height of the water layer, the slower the volatilization rate of the organic solvent. Emulsion liquid drops can spontaneously increase the interface area to induce an unstable phenomenon, and after the organic solvent is completely volatilized, the surfaces of the microspheres are solidified to form folds, so that the asymmetric Janus structure microspheres are obtained.
In a polymer mixed system, SDS has an amphiphilic property and can be adsorbed on an oil/water interface, and the interfacial tension of emulsion droplets is reduced due to surface shrinkage. CA further increases the interfacial area, under the combined action of the two, the interfacial tension can be reduced to zero or even negative, the interfacial instability phenomenon occurs, in addition, the cosurfactant can change the surface structure of the microsphere, and the surface of the liquid drop is sunken or protruded, so that the asymmetric Janus microsphere with the rough surface structure is formed.
Example 2
Roughness and ratio control
Regulation of polymer concentration
The roughness ratio of the asymmetric Janus structured polymeric microspheres can be controlled by varying the polymer concentration. The polymer used in the invention is a super-hydrophobic homopolymer, polystyrene is dissolved in toluene, cosurfactant CA is added, and the emulsion droplets are obtained after the cosurfactant CA and the water phase are fully mixed, the concentration of the polymer influences the density of the emulsion droplets, the higher the concentration of PS is, the higher the embedding liquid level ratio is, and the larger the roughness ratio of the obtained polymer microspheres is. As shown in FIGS. 1a to 1c, the CA concentration is 0.5mg/mL, the SDS concentration is 3mg/mL, the height h of the water layer in the volatilization device is 0.7mm, the PS concentrations are 10mg/mL, 15mg/mL and 20mg/mL, the microspheres are increased below the liquid surface along with the gradual increase of the PS concentration, the CA is adsorbed on the oil/water interface layer after the PS concentration is increased to a certain degree, the polymer microspheres are embedded in the liquid surface after the organic solvent toluene is completely volatilized, the interface instability phenomenon is generated, rough hemispheres with corrugation extending out on the surface are generated, and most asymmetric Janus microspheres are obtained after the surface is solidified. It can be seen that the polymer concentration has a significant effect on the roughness ratio of the Janus structure microspheres.
Example 3
Regulation of co-surfactant concentration
In the experiment, the influence of the CA concentration on the shape of the asymmetric Janus polymer microsphere is researched, and the concentration of n-hexadecanol is found to play an important role in controlling the roughness of the polymer microsphere. The volatilization rate of the organic solvent toluene is fixed, and the surface roughness of the polystyrene microsphere can be regulated and controlled by changing the concentration of CA. FIGS. 2a to 2c show asymmetric Janus microspheres with different roughness degrees obtained after the CA concentration is sequentially increased, wherein the height h of a fixed water layer is 0.7mm, the SDS concentration is 3mg/mL, the polymer PS concentration is 10mg/mL, and the concentrations of the cosurfactant CA are sequentially increased and are respectively 0.1mg/mL, 0.5mg/mL and 3.0 mg/mL. It can be seen that the roughness of the microspheres can be controlled by the concentration of CA, and the interfacial instability of emulsion droplets is greatly related to cosurfactant. Two main functions of CA are that the molecular adsorption of CA is accumulated in an oil/water interface layer to cause the reduction of interfacial tension; and the second is to cause the rearrangement of SDS molecules at the interface, further reduce the surface tension of emulsion droplets, and induce the phenomenon of interface instability by the combined action of SDS and the first. When the concentration of CA is increased to a certain degree, the emulsion droplets are subjected to explosive change, the surfaces of the microspheres are in flower shapes, and when the concentration of CA is 3mg/mL, the microspheres are not in spherical shapes any more, but are in large flower-shaped structures folded in sheet shapes. Therefore, the concentration of the cosurfactant CA has great influence on the preparation and the shape control of the Janus microspheres.
Example 4
Influence of the volatilization Rate of organic solvents
We also investigated the effect of the height h of the water layer in the volatilization device on the volatilization rate of the organic solvent. FIGS. 3a to 3c show polymer microspheres formed after toluene is completely volatilized as an organic solvent, and the preparation conditions are that the concentration of the polymer PS in toluene is 10mg/mL, the concentration of CA is 0.1mg/mL, and SDS solution of 3mg/mL is used as an aqueous phase. The height h of the water layer is 0.5mm, 0.7mm and 1.3mm respectively. The water layer is low in height, the organic solvent is high in volatilization rate, and the organic solvent is low in volatilization rate. When the volatilization rate of the organic solvent toluene is slow, the interface instability phenomenon occurs in a long period of time, and the surface of the microsphere slowly generates folds to gradually form flower-shaped microspheres; when the toluene volatilization rate is faster, the emulsion droplets spontaneously increase the interfacial area and freeze into coarse microspheres in a short time. As can be seen from FIGS. 3a to 3c, when the height of the water layer is 0.5mm and 0.7mm, the roughness of the microspheres is significant, and the increase of the height of the water layer is continued, the surface morphology of the microspheres is not significant, because the organic solvent is slowly volatilized and the roughened surface of the microspheres can be retracted into a smooth surface. It can be seen that the preparation of Janus microspheres is suitable for experiments at lower water layer heights.
Example 5
Effect of Co-solvent on asymmetric Janus microspheres
In the experimental exploration process, a method of adding a cosolvent is tried to regulate the density of emulsion droplets so as to control Janus microspheres with different roughness degrees. In a preliminary experiment, a cosolvent is mixed into a volatilization device, the cosolvent is quickly volatilized after being added, and the volatilization rate of an organic solvent is difficult to control; later, the solvents such as ethanol and acetone can be mutually soluble with toluene and xylene, namely, the cosolvents such as ethanol and acetone are added into the oil phase according to a certain proportion to prepare emulsion droplets, so that the roughness and proportion of the Janus microspheres are regulated and controlled.
The cosolvent is selected from solution with density smaller than water, such as ethanol, acetone, etc. The method has the main effects that the density of emulsion droplets is changed, the embedding degree of the emulsion droplets into the liquid surface is regulated and controlled, on the other hand, the volatilization rate of an organic solvent can be increased by adding the cosolvent, and most of the surfaces of the prepared asymmetric Janus microspheres are flower-shaped. The co-solvent selected in FIGS. 4 a-4 c was acetone, PS concentration was 10mg/mL, CA concentration was 1mg/mL, and the volume ratio of toluene to acetone was 1: 2,1: 1 and 5: 1. the preparation conditions of the microspheres in fig. 5 a-5 b are that the PS concentration is 10mg/mL, the CA concentration is 1mg/mL, the added cosolvent is ethanol, and the volume ratio of toluene to ethanol is 2:3,3: 2. experiments show that the larger the proportion of the added ethanol or acetone is, the smaller the proportion of the microspheres embedded in the liquid surface is, and the smaller the roughness proportion of the microspheres is.
The research on the cosolvent in the experiment shows that the asymmetric Janus structure microspheres can be well prepared after the ethanol and the acetone are added, the proportion of emulsion liquid drops embedded into the liquid level can be effectively controlled, and the larger the proportion of the cosolvent is, the larger the roughness degree is.
Example 6
The preparation method is the same as that of example 1, and chloroform is used as an organic solvent in the preparation process instead of toluene, so that the Janus microspheres with rough surfaces are not obtained, but the roughness of the whole microspheres can be controlled by regulating the concentration of hexadecanol, and the Janus microspheres with rough sides and smooth sides cannot be obtained. Experimental conditions as in the three graphs of fig. 6 a-6 c: the CA concentrations were varied to 0.6mg/mL, 1.3mg/mL, and 2.1mg/mL, respectively, with the SDS concentration being 3mg/mL and the PS concentration being 10 mg/mL.
In the application, an emulsion-solvent volatilization method is used for preparing the asymmetric Janus microspheres by utilizing the characteristic that the density of toluene is smaller than that of water and inducing the occurrence of an interface instability phenomenon. Emulsion droplets are prepared by a hand-shaking method, and parameters such as Polymer (PS) concentration, surfactant (SDS) concentration, Cosurfactant (CA) concentration, organic solvent volatilization rate, cosolvent proportion and the like are changed to regulate and control the roughness and proportion of the asymmetric Janus microspheres by utilizing the characteristic that toluene density is lower than water. The method is simple and effective, can prepare Janus microspheres with different roughness and proportions, and has good application prospects in the aspects of biological carriers, emulsion stability, optics, biosensing, catalysts and the like.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A preparation method of Janus microspheres is characterized in that an organic solvent with density less than that of water is used for dissolving a polymer and a cosurfactant as oil phases; dissolving a surfactant in ultrapure water to be used as a water phase; mixing the oil phase and the water phase, shaking uniformly to prepare emulsion liquid drops, placing the emulsion liquid drops below the liquid level of water in a volatilization device, standing for 1-24 hours at room temperature, sucking and precipitating by using a rubber-head dropper after the organic solvent is completely volatilized, collecting the precipitate into a centrifugal tube, standing for 24 hours, sucking out supernatant liquid by using the rubber-head dropper, adding ultrapure water for washing, and standing for 24 hours to obtain the Janus microspheres.
2. The method of claim 1, wherein the organic solvent is toluene, benzene and/or xylene.
3. The method of claim 1, wherein the polymer is polystyrene and/or polymethylmethacrylate.
4. The method of claim 1, wherein the surfactant is selected from the group consisting of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
5. The method of claim 1, wherein the co-surfactant is n-hexadecanol and/or n-octadecanol.
6. The preparation method of Janus microspheres as claimed in claim 1, wherein the volume ratio of the oil phase to the water phase is 1:10-1:1, the concentration of the polymer in the oil phase is 5-20mg/mL, the concentration of the cosurfactant is 0.5-3mg/mL, and the concentration of the water phase is 1-5 mg/mL.
7. The method for preparing Janus microspheres as claimed in claim 1, wherein the emulsion droplets are placed 0.5-1.5mm below the surface of water in the volatilization device.
8. The method for preparing Janus microspheres as claimed in claim 1, wherein the surface roughness structure of the Janus microspheres is adjusted by adjusting the concentrations of the organic solvent, the polymer, the cosurfactant, the surfactant and the height of emulsion droplets in water.
9. Janus microspheres prepared by the method of any one of claims 1-8.
CN201910482577.3A 2019-06-04 2019-06-04 Janus microsphere and preparation method thereof Pending CN110605075A (en)

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Application publication date: 20191224