CN116376313A - Preparation method and application of a responsive structured color droplet - Google Patents

Abstract

The invention belongs to the field of responsive structural color materials, and discloses a preparation method and application of responsive structural color liquid drops, wherein the preparation method specifically comprises the following steps: (1) Preparing a first surfactant solution and a second surfactant solution; (2) Preparing liquid hydrocarbon and liquid fluorocarbon as oil phase substances; (3) Uniformly mixing the first surfactant solution, the second surfactant solution, hydrocarbon and fluorocarbon to form an oil-in-water system, wherein the formed liquid drops are responsive structural color liquid drops; the mass ratio of the first surfactant to the second surfactant in the system is changed, so that the structural color of the liquid drop can appear or disappear, and the response of the structural color to the surfactant is realized. The structural color liquid drop can regulate and control the appearance of the liquid drop through the competitive action of the two surfactants, so that the display and disappearance of the structural color are controlled, the responsiveness is realized, and the method is very suitable for anti-counterfeiting.

Description

Preparation method and application of a responsive structured color droplet

technical field

The invention belongs to the field of responsive structural color materials, and more specifically relates to a preparation method and application of responsive structural color liquid droplets, which have the characteristic of surfactant response.

Background technique

Responsive structural color materials refer to materials that can change color under external stimuli such as temperature, humidity, electric field, and magnetic field. It can provide real-time feedback to external stimuli, and convert difficult-to-observe external stimuli into optical signals visible to the naked eye. Therefore, responsive structural color materials have great potential in the fields of intelligent display, anti-counterfeiting, information encryption, and biological detection.

However, the current responsive structural chromatic materials are mainly focused on responsive photonic crystal structural chromatic materials. At present, most of the preparation of photonic crystal materials still adopts the "top-down" strategy, such as photolithography and layer-by-layer deposition technology, to prepare large-scale materials. into desired micro-nanostructures. Although a variety of high-quality micro-nanostructures can be prepared by adopting a "top-down" strategy, this method has disadvantages such as high cost, material waste, low time efficiency, and limited structure size, which hinder its application in high-throughput applications. Applications. Therefore, developing new structural color materials and reducing their preparation cycle and cost are of great significance for further expanding the application of structural color materials.

Contents of the invention

In view of the above defects or improvement needs of the prior art, the purpose of the present invention is to provide a preparation method and application of responsive structural color droplets, wherein by improving and regulating the structure and composition of the droplets, two different Surfactant, the combination of the first surfactant, the second surfactant, hydrocarbons and fluorocarbons is used to obtain structurally colored liquid droplets. The structural color droplet can regulate the shape of the droplet through the competition of two surfactants, and then control the display and disappearance of the structural color to achieve responsiveness. The size and color of the structural color droplet obtained by the invention have randomness, can avoid being copied or imitated, and are very suitable for anti-counterfeiting. Moreover, the preparation process of the present invention is simple, and the raw materials are cheap and can be prepared in batches. In addition, similar to other structural colors, the structural color in the present invention has the advantages of anti-fading, environmental protection, and high saturation.

In order to achieve the above object, according to one aspect of the present invention, a method for preparing responsive structural color droplets is provided, which is characterized in that it includes the following steps:

(1) dissolving the first surfactant in deionized water to obtain the first surfactant solution; dissolving the second surfactant in deionized water to obtain the second surfactant solution; the first surfactant The solution and the second surfactant solution correspond to the aqueous solution of the continuous phase of the responsive structural color droplet; wherein, the first surfactant is FC-4430, FC301, Capstone FS-30, Capstone 62MA, ZY-FC327 , ZY-823, ZONLY FS300, TF282, TF328; the second surfactant is SDS, PVA, CTAB, F-108, F-127, TWEEN 20, TWEEN 40, TWEEN 60, TWEEN 80 a kind of

(2) Prepare liquid hydrocarbons and liquid fluorocarbons as oil phase substances; wherein, the density of the hydrocarbons is smaller than that of the fluorocarbons, the refractive index is larger than that of the fluorocarbons, and the hydrocarbons The compound and the fluorocarbon are immiscible with each other at room temperature; the hydrocarbon and the fluorocarbon correspond to the oil phase of the dispersed phase of the responsive structural color droplet;

(3) Mix the first surfactant solution, the second surfactant solution, the hydrocarbon and the fluorocarbon evenly to form an oil-in-water system, and the formed droplet is the response Structural color droplets; according to the mass ratio of the first surfactant and the second surfactant in the system, the droplets can have structural color or not;

When the mass ratio of the first surfactant to the second surfactant in the oil-in-water system satisfies 1:1 to 1:5, the form of the droplet is a Janus droplet with structural color;

When the mass ratio of the first surfactant to the second surfactant in the oil-in-water system does not satisfy 1:1-1:5, the liquid droplets do not have structural color.

As a further preference of the present invention, step (4) is also included:

When the mass ratio of the first surfactant to the second surfactant in the oil-in-water system satisfies 1:1 to 1:5, by adding the first surfactant solution and/or For the second surfactant solution, the mass ratio of the first surfactant and the second surfactant in the system deviates from 1:1 to 1:5, and the liquid droplets whose structural color disappears can be obtained by diffusion;

When in the oil-in-water system, the mass ratio of the first surfactant to the second surfactant does not satisfy 1:1～1:5, by adding the first surfactant to the oil-in-water system again solution and/or the second surfactant solution, so that the mass ratio of the first surfactant and the second surfactant in the system satisfies 1:1 to 1:5 again, and the liquid with structural color reproduction can be obtained by diffusion drop.

As a further preference of the present invention, in the step (1), the concentration of the first surfactant solution is 1-50 mg/mL, and the concentration of the second surfactant solution is 1-50 mg/mL.

As a further preference of the present invention, in the step (2), the hydrocarbon is stearyl methacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate One of esters, tert-butyl bromoacetate, n-butyl acrylate, and dodecyl acrylate;

The fluorocarbons are 1H,1H,2H,2H-heptadecafluorodecyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2-trifluoro One of ethyl methacrylate, hexafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, and trifluoroethyl methacrylate;

In the step (3), the volume ratio of the hydrocarbon to the fluorocarbon is 1:1˜1:8.

As a further preference of the present invention, in the step (3), the mixing is carried out in a vortex shaker, the oscillation speed is 300-2000rpm, and the oscillation time is 0.5-5min;

The diameter of the responsive structural color droplet is 20-200 μm.

According to another aspect of the present invention, the present invention provides the responsive structural color liquid droplet obtained by the above preparation method.

According to another aspect of the present invention, the present invention provides the application of the above-mentioned responsive structural color liquid droplet in anti-counterfeiting.

As a further preference of the present invention, specifically add the first surfactant solution and/or the second surfactant solution to the oil-in-water system again, so that the first surfactant and the second surfactant solution in the system The mass ratio deviates from or satisfies 1:1~1:5, and uses the diffusion effect to control the disappearance and reappearance of structural color.

Through the above technical scheme conceived by the present invention, compared with the prior art, two different surfactants are used, utilizing the coordination of the first surfactant, the second surfactant, hydrocarbons and fluorocarbons , to obtain responsive structural color droplets.

The present invention can precisely regulate the structural color by regulating the shape of the droplet to realize the responsiveness. The present invention uses these surfactants of FC-4430, FC301, Capstone FS-30, Capstone 62MA, ZY-FC327, ZY-823, ZONLY FS300, TF282, TF328 as the first surfactant, and these first surfactants can preferentially Reduce the interfacial tension between fluorocarbons and water; use SDS, PVA, CTAB, F-108, F-127, TWEEN 20, TWEEN 40, TWEEN 60, TWEEN 80 as the second surfactant, these The second surfactant is able to preferentially lower the interfacial tension between the hydrocarbon and water. By controlling the mass ratio of the first surfactant to the second surfactant in the system, the competition between the first surfactant and the second surfactant can be used to change the shape of the droplet and realize the structural color of the surfactant. the response to. Specifically, when the mass ratio of the first surfactant to the second surfactant in the system satisfies 1:1 to 1:5, the form of the droplet is a Janus droplet with structural color; when in the system, the first surface When the mass ratio of the active agent to the second surfactant does not satisfy 1:1 to 1:5, there is no structural color; thus, by controlling the mass ratio of the first surfactant to the second surfactant in the system, it is possible to make The droplet structure color appears or disappears, realizing the response.

The droplets in the present invention are composed of immiscible hydrocarbons and fluorocarbons. When the morphology of the droplets is Janus droplets, the density of hydrocarbons is lower than that of fluorocarbons, but the refractive index is greater than that of fluorocarbons. The characteristics of the compound can make liquid droplets produce structural color based on the combination of total internal reflection and interference mechanism.

Moreover, after mixing uniformly to form an oil-in-water system, the first surfactant solution and/or the second surfactant solution can be simply added to the system again without shaking again, and the diffusion effect of the water phase can be used to affect The interface between hydrocarbons and fluorocarbons in hydrocarbon-fluorocarbon droplets can further change the shape of the droplets and make the structural color of the droplets disappear or reappear. The structural color droplet with surfactant response obtained in the present invention can display and disappear the structural color by changing the mass ratio of the two surfactants several times to realize the cycle of displaying and disappearing the structural color.

Specifically, the present invention can obtain following beneficial effect:

(1) The preparation method of the structured color droplet provided by the present invention is simple, simple to operate, low in technical requirements, and can conveniently prepare the structured color droplet with controllable micro-nano size, and the required raw materials are cheap and easy to obtain, suitable for large-scale Production.

(2) The structural color droplets obtained in the present invention can realize the display and disappearance of structural color by adjusting the mass ratio of the two surfactants used. When the mass ratio is 1:1 to 1:5, the liquid droplets display structure color; when the mass ratio is outside 1:1 to 1:5, the structural color disappears, which is suitable for anti-counterfeiting and other fields.

(3) The structurally colored liquid droplets prepared by the present invention have the characteristics of being physically irreproducible, and are very suitable for anti-counterfeiting. Taking the formation of an oil-in-water system through oscillation treatment as an example, the overall condition of the droplets obtained by slight changes in the conditions during oscillation will change, which has characteristics that cannot be replicated physically.

Description of drawings

Figure 1 is the reflective mode optical microscope pictures of structural color droplets with different sizes prepared by the vortex mixing method in Example 1 and the reflective mode optical microscopes obtained by adding surfactant 1 and surfactant 2 in different situations picture.

Fig. 2 is the reflection mode optical microscope pictures of droplets with different sizes prepared by the vortex mixing method in Example 2 and the reflection mode optical microscope pictures of different situations obtained by adding surfactant 1 and surfactant 2 in cycles.

Figure 3 is the reflection mode optical microscope pictures of structural color droplets with different sizes prepared by the vortex mixing method in Example 3 and the reflection mode optical microscopes obtained by adding surfactant 1 and surfactant 2 in different situations picture.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.

Based on the present invention, the preparation method of the structured color droplet with surfactant response can be carried out according to the following steps:

(1) Configure a certain concentration of surfactant solution:

Configure a certain concentration of surfactant solution: respectively mix different surfactants of a certain quality (that is, surfactant 1, surfactant 2; the difference between the two is that surfactant 1 can preferentially reduce fluorocarbons and water The interfacial tension between the surfactant 2 can preferentially reduce the interfacial tension between hydrocarbons and water) dissolved in a certain volume of deionized water to obtain a continuous phase aqueous solution of responsive structural color droplets, and named it as Surfactant 1 solution and surfactant 2 solution; Surfactant 1 can be one of FC-4430, FC301, Capstone FS-30, Capstone62MA, ZY-FC327, ZY-823, ZONLY FS300, TF282, TF328, The concentration of the surfactant 1 can be 1-50mg/mL; the surfactant 2 can be one of SDS, PVA, CTAB, F-108, F-127, TWEEN 20, TWEEN 40, TWEEN 60, TWEEN 80 species, the concentration of the surfactant 2 can be 1-50mg/mL.

(2) Add hydrocarbons and fluorocarbons into the centrifuge tube according to a certain volume ratio. The hydrocarbon may be octadecyl methacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, tert-butyl bromoacetate, n-butyl acrylate, acrylic acid One of the dodecyl esters;

The fluorocarbons can be 1H,1H,2H,2H-heptadecafluorodecyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2-tri One of fluoroethyl methacrylate, hexafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, and trifluoroethyl methacrylate. The volume ratio of the hydrocarbons to the fluorocarbons may be 1:1˜1:8.

(3) Place the centrifuge tube containing hydrocarbons and fluorocarbons with a certain volume ratio in a vortex shaker, and set the oscillation speed so that the hydrocarbons and fluorocarbons can be fully mixed evenly to obtain a responsive structure The oil phase substance of the dispersed phase of the colored liquid droplets. The shaking speed can be 300-2000rpm, and the shaking time can be 0.5-5min.

(4) After hydrocarbons and fluorocarbons can be fully mixed and uniform, surfactant 1 and surfactant 2 with a certain mass ratio are added to the above solution, and the structural color liquid is prepared by vortex oscillator oscillation again drop. The prepared structural color droplet solution system was dropped on a watch glass, and the relationship between color and size was observed under a reflection mode optical microscope. The volume ratio of the oil phase substance to the surfactant solution may be 1:1˜1:20. The mass ratio of solute surfactant 1 to surfactant 2 can be 1:1～1:5, and the droplets obtained at this time will show structural color (of course, if the mass ratio of solute surfactant 1 to surfactant 2 If the ratio deviates from 1:1 to 1:5, the obtained droplets do not have structural color, and the structural color can be restored by adjusting the mass ratio of solute surfactant 1 to surfactant 2). The diameter of the structural color droplet is 20-200 μm.

The above-mentioned preparation process takes step (3) and step (4) to carry out the mixing of oil-phase substances respectively to form the mixing of the oil-in-water system as an example. In addition to mixing step by step, two kinds of surfactant aqueous solutions and two The two oil phase substances are added to the same centrifuge tube at one time, so that a well-mixed oil-in-water system can also be obtained after one shaking treatment. In addition, in addition to using a vortex oscillator to achieve mixing, other mixing methods such as hand shaking, ultrasonic mixing, and cell pulverizer treatment can also be used.

Further, in order to detect the responsiveness of the droplet, the following steps can be followed:

S1: Add a certain amount of surfactant 2 again to the liquid droplet solution system that has produced structural color, and observe the shape and color changes of the droplet through a reflection mode optical microscope. The quality of the re-added surfactant 2 needs to make the mass ratio of the solute surfactant 1 to the surfactant 2 in the whole system outside the range of 1:1-1:5.

S2: Add a certain amount of surfactant 1 again to the droplet solution system obtained in step S1, and observe the droplet morphology and color changes through a reflection mode optical microscope. The quality of the re-added surfactant 1 needs to make the mass ratio of the solute surfactant 1 to surfactant 2 in the whole system satisfy the range of 1:1-1:5.

S3: Steps S1 and S2 are repeated in sequence, and changes in droplet morphology and color are observed through a reflection mode optical microscope. The number of repeated cycles can reach more than 8 times.

Of course, in addition to first adding surfactant 2 to the system in step S1 and step S2 above, and then adding surfactant 1, it is also possible to add surfactant 1 first to make the mass of solute surfactant 1 and surfactant 2 If the ratio deviates from 1:1 to 1:5, then add surfactant 2 to restore the mass ratio of solute surfactant 1 to surfactant 2 to meet 1:1 to 1:5.

The following are specific examples:

Example 1

The structural color droplet in this embodiment is prepared according to the following method:

(1) Configure a certain concentration of surfactant solution:

A certain quality of Capstone FS-30 was dissolved in a certain volume of deionized water, and the concentration of the obtained CapstoneFS-30 aqueous solution (that is, surfactant 1 solution) was 15mg/mL; a certain quality of SDS was dissolved in a certain volume of In deionized water, the resulting aqueous SDS solution (ie, Surfactant 2 solution) had a concentration of 10 mg/mL; Surfactant 1 solution and Surfactant 2 solution could be used as aqueous solutions for the continuous phase of structurally colored droplets.

(2) Add ethoxylated trimethylolpropane triacrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate to a centrifuge tube according to a certain volume ratio, and the ethoxylated trimethylolpropane triacrylate The volume ratio of methylpropane triacrylate to 1H,1H,2H,2H-heptadecafluorodecyl acrylate is 1:1.

(3) Place the centrifuge tube containing ethoxylated trimethylolpropane triacrylate and 1H,1H,2H,2H-heptadecafluorodecyl acrylate with a volume ratio of 1:1 in a vortex shaker , set the oscillation speed to 500rpm, and the oscillation time to 1min, so that ethoxylated trimethylolpropane triacrylate and 1H,1H,2H,2H-heptadecafluorodecyl acrylate can be fully mixed evenly to obtain structural color droplets The oil phase substance of the dispersed phase.

(4) After the ethoxylated trimethylolpropane triacrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate can be fully mixed, the Capstone FS-30 aqueous solution with a certain mass ratio and SDS The aqueous solution was added to the above solution, and the structural color droplets were prepared by vortex shaking again. The prepared structural color droplet solution system was dropped on a watch glass, and the relationship between color and size was observed under a reflection mode optical microscope. The volume ratio of the oil phase substance and the surfactant solution is 1:5 (wherein, the volume of the surfactant solution is the volume algebra sum of the surfactant 1 solution and the surfactant 2 solution used in this step), solute The mass ratio of Capstone FS-30 to SDS is 1:2, and the diameter of the structural color droplet is 40-150 μm.

(5) A certain amount of Capstone FS-30 aqueous solution was added again to the droplet solution system that had produced structural color, and the shape and color changes of the droplet were observed through a reflection mode optical microscope. The quality of the re-added Capstone FS-30 needs to make the mass ratio of the solute Capstone FS-30 and SDS in the whole system to be 2:1.

(6) Add a certain amount of SDS aqueous solution again to the droplet solution system obtained in step (5), and observe the droplet morphology and color changes through a reflection mode optical microscope. The quality of the re-added SDS needs to make the mass ratio of the solute Capstone FS-30 and SDS in the whole system to be 1:2.

(7) Steps (5) and (6) were repeated in sequence, and the droplet morphology and color changes were observed through a reflection mode optical microscope. The number of repeated cycles is more than 8 times.

As shown in Figure 1, (a) in Figure 1 is an optical microscope picture that has produced structural color obtained in step (4), and at this time the mass ratio of solute Capstone FS-30 to SDS is 1:2; in Figure 1 (b) is after adding a certain amount of Capstone FS-30 aqueous solution in step (5) (the quality of the Capstone FS-30 that adds again at this moment makes the solute Capstone FS-30 of whole system and the mass ratio of SDS be 2:1 ) optical microscope picture, it can be seen that the structural color has disappeared. (c) in Fig. 1 is after adding a certain amount of SDS aqueous solution in step (6) (at this moment, the quality of the SDS that adds again makes the solute Capstone FS-30 of the whole system and the mass ratio of SDS be 1:2) From the optical microscope picture, it can be seen that the structural color reappears, and so on. The number of cycles can reach more than 8 times.

Example 2

The structural color droplet in this embodiment is prepared according to the following method:

(1) Configure a certain concentration of surfactant solution:

A certain quality of Capstone FS-30 was dissolved in a certain volume of deionized water, and the concentration of the obtained CapstoneFS-30 aqueous solution (that is, surfactant 1 solution) was 10mg/mL; a certain quality of SDS was dissolved in a certain volume of In deionized water, the resulting aqueous SDS solution (ie, Surfactant 2 solution) had a concentration of 20 mg/mL; Surfactant 1 solution and Surfactant 2 solution could be used as aqueous solutions for the continuous phase of structurally colored droplets.

(2) Add ethoxylated trimethylolpropane triacrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate to a centrifuge tube according to a certain volume ratio, and the ethoxylated trimethylolpropane triacrylate The volume ratio of methylpropane triacrylate to 1H,1H,2H,2H-heptadecafluorodecyl acrylate is 1:2.

(3) Place the centrifuge tube containing ethoxylated trimethylolpropane triacrylate and 1H,1H,2H,2H-heptadecafluorodecyl acrylate with a volume ratio of 1:2 in a vortex shaker , set the oscillation speed to 600rpm, and the oscillation time to 1min, so that ethoxylated trimethylolpropane triacrylate and 1H,1H,2H,2H-heptadecafluorodecyl acrylate can be fully mixed evenly to obtain structural color droplets The oil phase substance of the dispersed phase.

(4) After the ethoxylated trimethylolpropane triacrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate can be fully mixed, the Capstone FS-30 aqueous solution with a certain mass ratio and SDS The aqueous solution was added to the above solution, and the liquid droplets were prepared by shaking again with a vortex shaker. The prepared droplet solution system was dropped on a watch glass and observed under a reflection mode optical microscope. The volume ratio of the oil phase substance and the surfactant solution is 1:4 (wherein, the volume of the surfactant solution is the volume algebra sum of the surfactant 1 solution and the surfactant 2 solution used in this step), solute The mass ratio of Capstone FS-30 to SDS is 3:1, and the diameter of the droplet is 50-100 μm.

(5) A certain amount of SDS aqueous solution was added again to the above-mentioned droplet solution system, and the droplet morphology and color changes were observed through a reflection mode optical microscope. The quality of the re-added SDS needs to make the mass ratio of the solute Capstone FS-30 and SDS in the whole system to be 1:3.

(6) Add a certain amount of Capstone FS-30 aqueous solution to the droplet solution system obtained in step (5), and observe the droplet morphology and color changes through a reflection mode optical microscope. The quality of the re-added Capstone FS-30 needs to make the mass ratio of the solute Capstone FS-30 and SDS in the whole system to be 3:1.

(7) Steps (5) and (6) were repeated in sequence, and the droplet morphology and color changes were observed through a reflection mode optical microscope. The number of repeated cycles is more than 10 times.

As shown in Figure 2, (a) in Figure 2 is the optical microscope picture of the liquid droplet that does not produce structural color that step (4) obtains, and the mass ratio of solute Capstone FS-30 and SDS is 3:1 now; Fig. (b) in 2 is after adding a certain amount of SDS aqueous solution in step (5) (at this time, the quality of the SDS added again needs to make the mass ratio of the solute Capstone FS-30 and SDS of the whole system be 1:3) Optical microscope picture, it can be seen that the liquid droplets produce structural color. (c) among Fig. 2 is after adding a certain amount of Capstone FS-30 aqueous solution in step (6) (now, the quality of the Capstone FS-30 that adds again needs to make the solute Capstone FS-30 of whole system and the quality of SDS The optical microscope picture with a ratio of 3:1), it can be seen that the structural color disappears again, and so on. The number of cycles can reach more than 10 times.

Example 3

The structural color droplet in this embodiment is prepared according to the following method:

(1) Configure a certain concentration of surfactant solution:

A certain quality of Capstone FS-30 is dissolved in a certain volume of deionized water, and the concentration of the obtained CapstoneFS-30 aqueous solution (that is, surfactant 1 solution) is 20mg/mL; a certain quality of PVA is dissolved in a certain volume of In deionized water, the resulting aqueous PVA solution (ie, Surfactant 2 solution) had a concentration of 15 mg/mL; Surfactant 1 solution and Surfactant 2 solution could be used as aqueous solutions for the continuous phase of structurally colored droplets.

(2) Add ethoxylated trimethylolpropane triacrylate and 2,2,2-trifluoroethyl methacrylate into the centrifuge tube according to a certain volume ratio, and the ethoxylated trimethylolpropane triacrylate The volume ratio of methylpropane triacrylate to 2,2,2-trifluoroethyl methacrylate is 1:1.

(3) Place the centrifuge tube containing ethoxylated trimethylolpropane triacrylate and 2,2,2-trifluoroethyl methacrylate with a volume ratio of 1:1 in a vortex shaker , set the oscillation speed to 500rpm, and the oscillation time to 1min, so that ethoxylated trimethylolpropane triacrylate and 2,2,2-trifluoroethyl methacrylate can be fully mixed evenly to obtain structural color droplets The oil phase substance of the dispersed phase.

(4) After the ethoxylated trimethylolpropane triacrylate and 2,2,2-trifluoroethyl methacrylate can be fully mixed, the Capstone FS-30 aqueous solution with a certain mass ratio and PVA The aqueous solution was added to the above solution, and the structural color droplets were prepared by vortex shaking again. The prepared structural color droplet solution system was dropped on a watch glass, and the relationship between color and size was observed under a reflection mode optical microscope. The volume ratio of the oil phase substance and the surfactant solution is 1:5 (wherein, the volume of the surfactant solution is the volume algebra sum of the surfactant 1 solution and the surfactant 2 solution used in this step), solute The mass ratio of Capstone FS-30 to PVA is 2:3, and the diameter of the structural color droplet is 40-120 μm.

(5) A certain amount of Capstone FS-30 aqueous solution was added again to the droplet solution system that had produced structural color, and the shape and color changes of the droplet were observed through a reflection mode optical microscope. The quality of the re-added Capstone FS-30 needs to make the mass ratio of the solute Capstone FS-30 and PVA in the whole system to be 2:1.

(6) Add a certain amount of PVA aqueous solution again to the droplet solution system obtained in step (5), and observe the droplet morphology and color changes through a reflection mode optical microscope. The quality of the PVA added again needs to make the mass ratio of the solute Capstone FS-30 and PVA in the whole system be 2:3.

(7) Steps (5) and (6) were repeated in sequence, and the droplet morphology and color changes were observed through a reflection mode optical microscope. The number of repeated cycles is more than 10 times.

As shown in Figure 3, (a) in Figure 3 is the optical microscope picture that has produced structural color that step (4) obtains, and the mass ratio of solute Capstone FS-30 and PVA is 2:3 at this moment; (b) is after adding a certain amount of Capstone FS-30 aqueous solution in step (5) (at this moment, the quality of the Capstone FS-30 that adds again needs to make the solute Capstone FS-30 of whole system and the mass ratio of PVA be 2 :1) Optical microscope pictures, it can be seen that the structural color has disappeared. (c) in Figure 3 is after adding a certain amount of PVA aqueous solution in step (6) (at this time, the quality of the PVA added again needs to make the mass ratio of the solute Capstone FS-30 of the whole system to PVA be 2:3) From the optical microscope picture, it can be seen that the structural color reappears, and so on. The number of cycles can reach more than 10 times.

The above-mentioned embodiment is only an example, in addition to the examples above, the surfactant 1 can also be any one of FC-4430, FC301, Capstone 62MA, ZY-FC327, ZY-823, ZONLY FS300, TF282, TF328 , these surfactants are similar to Capstone FS-30 and can preferentially reduce the interfacial tension between fluorocarbons and water; Surfactant 2 can also be CTAB, F-108, F-127, TWEEN 20, TWEEN 40, Any one of TWEEN 60 and TWEEN 80, these surfactants are similar to SDS and PVA, and can preferentially reduce the interfacial tension between hydrocarbons and water; specific types of hydrocarbons, specific types of fluorocarbons, It can also be adjusted flexibly, as long as they are all liquid at room temperature and are immiscible with each other, the density of hydrocarbons is lower than that of fluorocarbons, and the refractive index is higher than that of fluorocarbons. In addition, the preparation process and subsequent detection process of each of the above-mentioned examples are all carried out at room temperature.

It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.

Claims (8)

1. A method for preparing responsive structural color droplets, comprising the steps of:

(1) Dissolving a first surfactant in deionized water to obtain a first surfactant solution; dissolving a second surfactant in deionized water to obtain a second surfactant solution; the first surfactant solution and the second surfactant solution correspond to aqueous solutions of continuous phases of responsive structural color droplets; wherein the first surfactant is one of FC-4430, FC301, capstone FS-30, capstone 62MA, ZY-FC327, ZY-823, ZONLY FS300, TF282 and TF 328; the second surfactant is one of SDS, PVA, CTAB, F-108, F-127, TWEEN20, TWEEN 40, TWEEN 60 and TWEEN 80;

(2) Preparing liquid hydrocarbon and liquid fluorocarbon as oil phase substances; wherein the hydrocarbon has a density less than the fluorocarbon, a refractive index greater than the fluorocarbon, and the hydrocarbon and the fluorocarbon are immiscible at room temperature; an oil phase material of the hydrocarbon and the fluorocarbon corresponding to the dispersed phase of the responsive structural color droplets;

(3) Uniformly mixing the first surfactant solution, the second surfactant solution, the hydrocarbon and the fluorocarbon to form an oil-in-water system, wherein the formed liquid drops are responsive structural color liquid drops; according to the mass ratio of the first surfactant to the second surfactant in the system, the liquid drops can have structural colors or not;

when the mass ratio of the first surfactant to the second surfactant in the oil-in-water system is 1:1-1:5, the liquid drops are Janus liquid drops and have structural colors;

when the mass ratio of the first surfactant to the second surfactant in the oil-in-water system is not 1:1-1:5, the liquid drops do not have structural color.

2. The method of producing a responsive structural color drop of claim 1, further comprising the step (4):

when the mass ratio of the first surfactant to the second surfactant in the oil-in-water system is 1:1-1:5, adding the first surfactant solution and/or the second surfactant solution into the oil-in-water system again to enable the mass ratio of the first surfactant to the second surfactant in the system to deviate from 1:1-1:5, and obtaining liquid drops with disappeared structural color by utilizing diffusion;

when the mass ratio of the first surfactant to the second surfactant in the oil-in-water system does not meet 1:1-1:5, the first surfactant solution and/or the second surfactant solution are added into the oil-in-water system again, so that the mass ratio of the first surfactant to the second surfactant in the system meets 1:1-1:5 again, and the liquid drops with the structural color reproduction can be obtained by utilizing the diffusion effect.

3. The method of claim 1, wherein in step (1), the concentration of the first surfactant solution is 1 to 50mg/mL, and the concentration of the second surfactant solution is 1 to 50mg/mL.

4. The method for producing a responsive structural color droplet according to claim 1, wherein in the step (2), the hydrocarbon is one of octadecyl methacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, t-butyl bromoacetate, n-butyl acrylate, dodecyl acrylate;

the fluorocarbon is 1H, 2H-heptadecafluorodecyl acrylate 1, 3-hexafluoroisopropyl methacrylate 2, 2-trifluoroethyl methacrylate one of hexafluorobutyl methacrylate, 2,3, 4-hexafluorobutyl acrylate and trifluoroethyl methacrylate;

in the step (3), the volume ratio of the hydrocarbon to the fluorocarbon is 1:1-1:8.

5. The method for producing a responsive structural color droplet according to claim 1, wherein in the step (3), the mixing is performed in a vortex oscillator at a vibration speed of 300 to 2000rpm for a vibration time of 0.5 to 5min;

the diameter of the responsive structural color drop is 20-200 mu m.

6. Responsive structural color droplets obtained by the method of any one of claims 1 to 5.

7. The use of the responsive structural color drop of claim 6 in anti-counterfeiting.

8. The use according to claim 7, wherein the first surfactant solution and/or the second surfactant solution is added to the oil-in-water system again to provide a first surface in the system

The mass ratio of the surfactant to the second surfactant deviates from or meets 1:1-1:5, and by utilizing the diffusion effect,

the disappearance and reproduction of the structural color is controlled.

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