Preparation methods of fluorocarbon / hydrocarbon oil gel microspheres with various structural configurations
By using a mixture of hydrocarbon and fluorocarbon gelling solvents and surfactants, fluorocarbon/hydrocarbon oleogel microspheres with various structures were prepared, solving the problems of limited functionality and complex preparation of existing gel materials, and achieving high gas solubility, chemical stability and self-cleaning ability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YANGZHOU UNIV
- Filing Date
- 2026-04-15
- Publication Date
- 2026-07-17
AI Technical Summary
Existing gel materials have limited functionality, complex and costly preparation processes, and existing fluorocarbon/hydrocarbon oil gel microspheres have limitations in solvent selection and application.
Using hydrocarbon and fluorocarbon compound gelling solvents, and by adding specific gelling agents and surfactants, fluorocarbon/hydrocarbon oleogel microspheres are prepared by mixing under heat preservation conditions to form droplet templates and then allowing them to stand in an ice bath, thus achieving a variety of structural configurations.
The prepared fluorocarbon/hydrocarbon oil gel microspheres have high gas solubility, hydrophobicity, chemical stability and multifunctionality. They can load hydrophilic and hydrophobic molecules to achieve differentiated release, have self-cleaning ability and tunable structure.
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Figure CN122399692A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of gel materials technology, specifically relating to a method for preparing fluorocarbon / hydrocarbon oil gel microspheres. Background Technology
[0002] In the development trend of modern materials science, materials design is shifting from achieving single properties to synergistic effects of composite structures and multifunctionality. Fluorinated gels refer to gel systems incorporating fluorine elements or fluorine groups into a polymer network. The high electronegativity of fluorine atoms and the low polarity of the overall molecule endow the material with unique properties: high hydrophobicity, low surface energy, high chemical and thermal stability, and a great ability to absorb gases. Gel microspheres refer to spherical polymer particles with a scale ranging from nanometers to micrometers, whose cross-linked networks fully expand in solvents to form colloidal particles. As cross-linked polymer particles with a scale ranging from nanometers to micrometers, the core advantages of gel microspheres lie in their rapid stimulus response (such as sensitivity to temperature and pH changes) and huge specific surface area.
[0003] Existing traditional single-component gel materials suffer from limitations in functionality. For example, patent application CN111793244A discloses a method for preparing supramolecular perfluorinated gels, but this technology relies on a macroscopic system, fails to achieve microscale scaling of fluorocarbon compound gelling solvents, and the preparation process involves expensive equipment, difficult operation, and high costs. Patent application CN108504006A discloses a silica aerogel / organofluoropolymer composite film that is overly functionalized and has a limited market application. Patent application CN 118925607A discloses a Janus organic microgel that, while possessing a simple silicone oil / vegetable oil dual-gel structure, its oil phase selection is limited to conventional oils, not solvents with high solubility for drug molecules. Compared to fluorocarbon / hydrocarbon oil gel microspheres, it has fewer functions, and the gelling agent used is naturally occurring. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing fluorocarbon / hydrocarbon oleogel microspheres with various structural configurations, so as to overcome the shortcomings of the prior art. The prepared fluorocarbon / hydrocarbon oleogel microspheres have good anti-degradation properties, long-term stability and high safety.
[0005] Therefore, the technical solution to achieve the purpose of this invention is as follows: A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with various structural configurations, comprising the following steps: (S1) Synthesis of 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent, the reaction formula is as follows: ; (S2) Synthesis of diperfluorohexyl ethyl terephthalate gelling agent, the reaction formula is as follows: ; (S3) Under heating conditions, add the gelling agent 2,5-pyridinedicarboxylic acid di(hexadecyl) ester to a hydrocarbon gelling solvent until clear, and add the gelling agent diperfluorohexyl ethyl terephthalate to a fluorocarbon compound gelling solvent until clear; (S4) Under heat preservation conditions, the two clarified liquids obtained in step (S3) are vortex-mixed with an aqueous solution containing surfactant to obtain droplet templates; (S5) The droplet template is placed in an ice bath to prepare fluorocarbon / hydrocarbon oil gel microspheres.
[0006] Further, step (S1) includes the following sub-steps: (S1-1) Under room temperature and nitrogen protection, 4-dimethylaminopyridine was slowly added to a stirred suspension of 2,5-pyridinedicarboxylic acid in toluene. After stirring and mixing, hexadecyl alcohol and triethylamine were added in sequence, and the temperature was raised to 100°C and heated to reflux. After the (S1-2) reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, the residue was dissolved in dichloromethane and washed with water several times; the oil phase was dried over anhydrous sodium sulfate and concentrated, and the crude product was purified by silica gel column chromatography to obtain a pale yellow solid, 2,5-pyridinedicarboxylic acid di(hexadecyl) ester.
[0007] Further, in step (S1-1), the stirring time is 10 minutes and the heating reflux time is 48 hours; in step (S1-2), the eluent for silica gel column chromatography is n-hexane and dichloromethane in a volume ratio of 3:1.
[0008] 4. The method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to claim 1, characterized in that: step (S2) includes the following sub-steps: (S2-1) Under room temperature and nitrogen protection, 4-dimethylaminopyridine was slowly added to a stirred suspension of 1H,1H-pentadecafluorooctanol in toluene. After stirring and mixing, terephthaloyl chloride and triethylamine were added in sequence, and the mixture was heated to 100°C and refluxed. (S2-2) After the reaction is completed, the reaction solution is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, the residue is dissolved in dichloromethane and washed with water several times; the organic phase is dried over anhydrous sodium sulfate and concentrated, and the crude product is purified by silica gel column chromatography to obtain a white solid compound, diperfluorohexyl ethyl terephthalate.
[0009] Further, in step (S2-1), the stirring time is 10 minutes; the heating reflux time is 48 hours; in step (S2-2), the eluent for silica gel column chromatography is n-hexane and dichloromethane in a volume ratio of 3:1.
[0010] Further, the hydrocarbon gelling solvent is selected from n-pentane, n-hexane, n-heptane, or n-octane; the fluorocarbon compound gelling solvent is selected from perfluorinated mixture FC-770, ethyl perfluorobutyl ether (HFE7200), or perfluorooctane; and the surfactant is selected from Tween 20, cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium bromide (CTAB), DuPont FS-30 (FS-30), or sodium dodecyl sulfate (SDS).
[0011] Furthermore, in steps (S3) and (S4), the heating temperature is 80~95℃, and the mixing method is to gently shake or use a rotor as a stirrer with a speed of 50-100 rpm.
[0012] Further, in step (S3), the volume ratio of hydrocarbon gelling solvent to fluorocarbon compound gelling solvent is 1:(0.1-10); the 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent accounts for 3-10 wt% of the hydrocarbon gelling solvent; and the diperfluorohexyl ethyl terephthalate gelling agent accounts for 10-20 wt% of the fluorocarbon compound gelling solvent.
[0013] Further, in step (S4), the surfactant has a mass fraction of 0.5~10wt% in the aqueous solution; the total volume ratio of hydrocarbon gelling solvent and fluorocarbon compound gelling solvent to the surfactant solution is 1:(1~10).
[0014] Furthermore, in step (S5), the settling time during the ice bath is 0.5h-10h.
[0015] This invention utilizes two immiscible solvents: hydrocarbon-based gelling solvents and fluorocarbon-based gelling solvents. Different types of gelling agents are added to these two immiscible solvents, followed by an aqueous solution containing surfactants. Heating dissolves the different types of gelling agents in both the hydrocarbon and fluorocarbon gelling solvents. The mixture is then vortexed under insulated conditions. After droplet formation stabilized by surfactant molecules, fluorocarbon / hydrocarbon oleogel microspheres are prepared using an ice bath. Compared to existing technologies, the advantages of this invention are: the fluorocarbon / hydrocarbon oleogel microspheres construct various structures of composite gels of fluorocarbon and hydrocarbon gelling solvents at the microscale, such as core-shell and "snowman" shapes. The fluorinated gel imparts high gas solubility, high hydrophobicity, and high chemical stability to the microspheres. This material can simultaneously load hydrophilic and hydrophobic molecules, achieving differentiated release. The fluorinated fragments produced during degradation also possess surface activity, endowing the system with self-cleaning capabilities. The performance advantages of the fluorocarbon / hydrocarbon oleogel microspheres are reflected in multiple aspects. By adjusting parameters such as the ratio of the two phases and the crosslinking density, the interfacial properties can be precisely controlled, especially the hydrophobicity, gas adsorption, and interfacial behavior of the fluorinated gel region can be independently regulated. The preparation process of this invention is simple and can be used to prepare a series of fluorocarbon / hydrocarbon oil gel microspheres in batches.
[0016] The fluorocarbon / hydrocarbon oleogel microspheres of this invention possess excellent multi-zone structure, superior thermal and chemical stability, high specific surface area, unique gas dissolution and transport capabilities, stimulus responsiveness, and structural tunability. Furthermore, their designable multi-zone fluorinated and hydrocarbon gel structures enable differentiated interfacial properties and functions. The presence of the fluorinated gel gives them unique application potential in gas trapping, oil-water separation, and self-cleaning scenarios. This structural controllability allows the gel microspheres to exhibit different physical or chemical properties in different directions, providing an ideal platform for multifunctional integration. Scanning electron microscopy characterization further confirms the clear internal structure of the gel microspheres. This invention not only provides new ideas for research on fluorocarbon / hydrocarbon oleogel microspheres but also promotes their development and application in fields such as pollutant treatment, battery energy, drug delivery, and materials science. Attached Figure Description
[0017] Figure 1 Schematic diagram of the preparation process of fluorocarbon / hydrocarbon oil gel microspheres.
[0018] Figure 2 Schematic diagram of the synthesis pathway of gelling agents.
[0019] a) Synthetic route of fluorinated gelling agent (diperfluorohexyl ethyl terephthalate); b) Synthetic route of alkane gelling agent 2,5-pyridinedicarboxylic acid di(hexadecyl) ester.
[0020] Figure 3Microscopic observation and macroscopic morphology comparison of droplets and gel microspheres.
[0021] A and C are microscopic images of droplet systems formed under different surfactant ratios and their corresponding macroscopic states; where A: 4wt% CTAC; B: 0.5wt% CTAC + 4wt% FS30; C: 2wt% FS30.
[0022] A'-C' are microscopic images and macroscopic views of fluorocarbon / hydrocarbon oil gel microspheres formed by gelation based on the above droplets as templates. The scale bar is 100 μm.
[0023] Figure 4 SEM image of a single-phase macroscopic gel.
[0024] a) An alkane macrogel formed using n-heptane as solvent and 5 wt% di(hexadecyl) 2,5-pyridinedicarboxylate as gelling agent; b) Fluorocarbon macrogel formed using FC-770 as solvent and 10wt% diperfluorohexyl terephthalate gelling agent.
[0025] Figure 5 SEM characterization: Microstructure of fluorocarbon / hydrocarbon oleogel microspheres.
[0026] a, c) Low-magnification and locally magnified SEM images of gel microspheres prepared in a system with 4 wt% CTAC surfactant; (b, d) Low-magnification and locally magnified SEM images of gel microspheres prepared in a system with 4 wt% FS30 surfactant.
[0027] Both systems exhibit clear structures of fluorocarbon and hydrocarbon gelling solvents.
[0028] Figure 6 The stability and morphological evolution of fluorocarbon / hydrocarbon oil gel microspheres over time.
[0029] Microscopic and macroscopic images of the gel microspheres at different time points (a: 0h, b: 5h, c: 12h, d: 24h, e: 36h, f: 50h) at room temperature in a heptane / FC770 / 4wt%CTAC (volume ratio 1 / 1 / 4) system. The results show that the gel microspheres maintain structural integrity and stability over a long period. Scale bar: 100 μm. Detailed Implementation
[0030] The present invention will now be described in further detail with reference to specific embodiments and accompanying drawings. Example 1
[0031] First, the 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent was synthesized, and the reaction formula is as follows: ; Specifically, under nitrogen protection at room temperature, 4-dimethylaminopyridine (DMAP) was slowly added to a stirred suspension of 2,5-pyridinedicarboxylic acid in toluene. After stirring for 10 minutes, hexadecyl alcohol and triethylamine were added sequentially, the mixture was heated to 100°C and refluxed for 48 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, the product was dissolved in dichloromethane, and washed repeatedly with water. The crude product was purified by silica gel column chromatography (n-hexane / dichloromethane, 3:1) to obtain a pale yellow solid compound, di(hexadecyl) 2,5-pyridinedicarboxylic acid.
[0032] The diperfluorohexyl ethyl terephthalate gelling agent is then synthesized, and the reaction formula is as follows: ; Specifically, under nitrogen protection at room temperature, 4-dimethylaminopyridine (DMAP) was slowly added to a stirred solution of 1H,1H-pentadecafluorooctanol in toluene. After 10 minutes, terephthaloyl chloride and triethylamine were added sequentially, and the mixture was stirred at 100°C for 48 hours. After the reaction was complete, the mixture was cooled to room temperature, volatile substances were removed under reduced pressure, the product was dissolved in dichloromethane, and washed repeatedly with water. The crude product was purified by silica gel column chromatography (n-hexane / dichloromethane, 3:1) to give a white solid compound, diperfluorohexyl ethyl terephthalate.
[0033] The 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent and the diperfluorohexyl terephthalate ethyl ester gelling agent used below were prepared according to the above method.
[0034] The effect of different surfactant compositions on the preparation of fluorocarbon / hydrocarbon oil gel microspheres: Take three capped glass sample vials, transfer 300 μL of FC-770 (fluorocarbon gelling solvent), and add 1200 μL of 4wt% CTAC (hexadecyltrimethylammonium chloride) aqueous solution, 0.5wt% CTAC and 4wt% FS-30 aqueous solution, and 2wt% FS-30 aqueous solution respectively according to different surfactant compositions. Transfer and add 300 μL of n-heptane (hydrocarbon gelling solvent), and mix by vortexing at 3500 rpm for 3 min. After the surfactant molecules stabilize and form droplets, incubate on ice for 0.5 h, and take microscopic images of each droplet using an optical microscope.
[0035] The results are as follows Figure 3As shown in Figures A and C, these are microscopic and macroscopic images of the droplet. The structure using a 4wt% CTAC aqueous solution is a shell-core structure where n-heptane completely encapsulates FC-770. The structure using a 0.5wt% CTAC and 4wt% FS-30 aqueous solution is a snowman-like structure composed of n-heptane hemispheres and FC-770 hemispheres. The structure using a 2wt% FS-30 aqueous solution is a shell-core structure where FC-770 completely encapsulates n-heptane.
[0036] Take three capped glass sample vials, and under heating at 80°C, transfer 300 μL of FC-770 (a fluorocarbon gelling solvent). Add diperfluorohexyl ethyl terephthalate gelling agent at a mass ratio of 10 wt% until clear. Add 1200 μL of 4 wt% CTAC aqueous solution, 0.5 wt% CTAC and 4 wt% FS-30 aqueous solution, and 2 wt% FS-30 aqueous solution, respectively, according to different surfactant compositions. Under heating at 80°C, transfer and add 300 μL of n-heptane (a hydrocarbon gelling solvent), and then add di(hexadecyl) 2,5-pyridinedicarboxylate gelling agent at a mass ratio of 5 wt% until clear. Mix under vortex oscillation at 3500 rpm for 3 min, protected by an insulating sleeve structure. After the surfactant molecules stabilize and form droplets, incubate on ice for 0.5 h to stabilize and prepare fluorocarbon / hydrocarbon oil gel microspheres. Take microscopic images of each fluorocarbon / hydrocarbon oil gel microsphere using an optical microscope.
[0037] The results are as follows Figure 3 As shown in Figures A'-C', these are microscopic and macroscopic images of fluorocarbon / hydrocarbon oil gel microspheres. Figure A' corresponds to a surfactant composition of 4wt% CTAC. The morphology of the fluorocarbon / hydrocarbon oil gel microspheres is the same as the droplet structure of the corresponding surfactant composition, both exhibiting a shell-core structure where the n-heptane gel region completely encloses the FC-770 gel region. Figure B' corresponds to a surfactant composition of 0.5wt% CTAC and 4wt% FS-30. The morphology of the fluorocarbon / hydrocarbon oil gel microspheres is the same as the droplet structure of the corresponding surfactant composition, both exhibiting a snowman-like structure composed of n-heptane gel hemispheres and FC-770 gel hemispheres. Figure C' corresponds to a surfactant composition of 2wt% FS-30. The morphology of the fluorocarbon / hydrocarbon oil gel microspheres is the same as the droplet structure of the corresponding surfactant composition, both exhibiting a shell-core structure where the FC-770 gel region completely encloses the n-heptane alkane gel region. It can be seen that the droplets and fluorocarbon / hydrocarbon oil gel microspheres have the same morphology and particle size, indicating that the droplets can be used to prepare fluorocarbon / hydrocarbon oil gel microspheres, and the morphology of the composite gel microspheres can be controlled by changing the surfactant. Example 2
[0038] Preparation and micromorphology analysis of macroscopic gels of different phases Take a capped glass sample vial, heat it at 80°C, and add 300 μL of n-heptane (a hydrocarbon gelling solvent). Then, add 5 wt% of di(hexadecyl) 2,5-pyridinedicarboxylate gelling agent until the solution is clear. Take another capped glass sample vial, heat it at 80°C, and add 300 μL of FC-770 (a fluorocarbon gelling solvent). Add 10 wt% of diperfluorohexyl terephthalate gelling agent until the solution is clear. Mix the samples under vortex oscillation at 3500 rpm for 3 min, protected by an insulated jacket. After 0.5 h in an ice bath, obtain the n-heptane macrogel and the FC-770 macrogel. Pre-treat the macrogels at -5°C. After pre-treating, freeze-dry the samples under vacuum (freeze-drying temperature -60°C) to obtain the dry gels of the n-heptane macrogel and the FC-770 macrogel. Observe the microstructure of the samples using scanning electron microscopy (SEM).
[0039] The results are as follows Figure 4 As shown, Figure 4 Figure a corresponds to the SEM image of the microstructure of the n-heptane macrogel, which has a layered structure. Figure b corresponds to the SEM image of the microstructure of the FC-770 macrogel, which has a sheet-like structure. Example 3
[0040] Comparison of SEM morphology of fluorocarbon / hydrocarbon oil gel microspheres with different surfactant systems: Two capped glass sample vials were heated at 80°C. 300 μL of FC-770 (a fluorocarbon gelling solvent) was transferred, and diperfluorohexyl ethyl terephthalate gelling agent was added at a mass ratio of 10 wt% until the solution was clear. Then, 1200 μL of 4 wt% CTAC aqueous solution and 4 wt% FS-30 aqueous solution (surfactants) were added respectively. After heating at 80°C, 300 μL of n-heptane (a hydrocarbon gelling solvent) was added, followed by 5 wt% di(hexadecyl) 2,5-pyridinedicarboxylate gelling agent until the solution was clear. The mixture was vortexed at 3500 rpm for 3 min under a heat-insulating jacket for protection. After the surfactant molecules stabilized and formed droplets, the mixture was placed in an ice bath for 0.5 h to stabilize and prepare fluorocarbon / hydrocarbon oil gel microspheres. The microspheres were then frozen at -5°C. After the freeze-drying pretreatment, the sample was freeze-dried under vacuum at a temperature of -60℃ to obtain a dry gel. The microstructure of the sample was observed using a scanning electron microscope (SEM).
[0041] The results are as follows Figure 5 As shown: Figure 5 a is a gel microsphere prepared using the system of n-heptane / FC-770 / 4wt%CTAC=1 / 1 / 4. Figure 5b represents gel microspheres prepared using a system of n-heptane / FC-770 / 4wt%FS30 = 1 / 1 / 4. Figure 5 c is Figure 5 A partial scale-up of system a Figure 5 d is Figure 5 Local scale-up of system b. Figure 5 a, Figure 5 c. The gel microspheres have a layered structure completely encapsulated by n-heptane, and they have a good pore structure. Figure 5 b,5d gel microspheres exhibit a sheet-like structure completely encapsulated by FC-770. This demonstrates that the morphology of the double-sided gel microspheres can be controlled by altering the surfactant. Example 4
[0042] Morphological evolution of fluorocarbon / hydrocarbon oil gel microspheres at different times Take a capped glass sample vial, heat it at 80℃, and add 300 μL of FC-770 (fluorocarbon gelling solvent). Add diperfluorohexyl ethyl terephthalate gelling agent at a mass ratio of 10 wt% until clear. Add 1200 μL of 4 wt% CTAC aqueous solution, heat it at 80℃, and add 300 μL of n-heptane (hydrocarbon gelling solvent). Then, add di(hexadecyl) 2,5-pyridinedicarboxylate gelling agent at a mass ratio of 5 wt% until clear. Mix the vials at 3500 rpm for 3 min using an insulated sleeve structure. After the droplets are stabilized by surfactant molecules, incubate them in an ice bath for 0.5 h to obtain stable fluorocarbon / hydrocarbon oil gel microspheres. Take microscopic images of each droplet at 0 h, 5 h, 12 h, 24 h, 36 h, and 50 h using an optical microscope.
[0043] The results are as follows Figure 6 As shown: Figure 6 All gel microspheres were prepared using a heptane / FC-770 / 4wt%CTAC = 1 / 1 / 4 system. Figure a represents 0 h, Figure b represents 5 h, Figure c represents 12 h, Figure d represents 24 h, Figure e represents 36 h, and Figure f represents 50 h. Microscopically, the microspheres consistently maintained a shell-core structure where heptane completely encapsulated FC-770, exhibited good dispersion and uniform size distribution, and remained stable over a long period.
[0044] The hydrocarbon gelling solvent in the above embodiments can be selected from n-pentane, n-hexane, n-heptane, or n-octane; the fluorocarbon compound gelling solvent can be selected from perfluorinated mixture FC-770, ethyl perfluorobutyl ether (HFE7200), or perfluorooctane; the surfactant can be selected from Tween 20, cetyltrimethylammonium chloride (CTAC), cetyltrimethylammonium bromide (CTAB), DuPont FS-30 (FS-30), or sodium dodecyl sulfate (SDS).
[0045] Under heating conditions, di(hexadecyl) 2,5-pyridinedicarboxylate, a gelling agent, is added to a hydrocarbon gelling solvent until clear. Di(perfluorohexyl) ethyl terephthalate, a gelling agent, is added to a fluorocarbon gelling solvent until clear. The volume ratio of the hydrocarbon gelling solvent to the fluorocarbon gelling solvent is 1:(0.1–10); the 2,5-pyridinedicarboxylate gelling agent accounts for 3–10 wt% of the hydrocarbon gelling solvent; the di(perfluorohexyl) ethyl terephthalate gelling agent accounts for 10–20 wt% of the fluorocarbon gelling solvent. During vortex mixing, the temperature can be 80–95°C, and the mixing method is gentle shaking or using a rotor as a stirrer at a speed of 50–100 rpm. The surfactant has a mass fraction of 0.5–10 wt% in the aqueous solution; the total volume ratio of the hydrocarbon gelling solvent and the fluorocarbon gelling solvent to the surfactant solution is 1:(1–10).
Claims
1. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations, characterized in that, Includes the following steps: (S1) Synthesis of 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent, the reaction formula is as follows: ； (S2) Synthesis of diperfluorohexyl ethyl terephthalate gelling agent, the reaction formula is as follows: ； (S3) Under heating conditions, add the gelling agent 2,5-pyridinedicarboxylic acid di(hexadecyl) ester to a hydrocarbon gelling solvent until clear, and add the gelling agent diperfluorohexyl ethyl terephthalate to a fluorocarbon compound gelling solvent until clear; (S4) Under heat preservation conditions, the two clarified liquids obtained in step (S3) are vortex-mixed with an aqueous solution containing surfactant to obtain droplet templates; (S5) The droplet template is placed in an ice bath to prepare fluorocarbon / hydrocarbon oil gel microspheres.
2. The method for preparing fluorocarbon / hydrocarbon oleogel microspheres with multiple structural configurations according to claim 1, characterized in that: Step (S1) includes the following sub-steps: (S1-1) Under room temperature and nitrogen protection, 4-dimethylaminopyridine was slowly added to a stirred suspension of 2,5-pyridinedicarboxylic acid in toluene. After stirring and mixing, hexadecyl alcohol and triethylamine were added in sequence, and the temperature was raised to 100°C and heated to reflux. After the (S1-2) reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, the residue was dissolved in dichloromethane and washed with water several times; the oil phase was dried over anhydrous sodium sulfate and concentrated, and the crude product was purified by silica gel column chromatography to obtain a pale yellow solid, 2,5-pyridinedicarboxylic acid di(hexadecyl) ester.
3. The method for preparing fluorocarbon / hydrocarbon oleogel microspheres with multiple structural configurations according to claim 2, characterized in that: In step (S1-1), the stirring time is 10 minutes and the heating reflux time is 48 hours; in step (S1-2), the eluent for silica gel column chromatography is n-hexane and dichloromethane in a volume ratio of 3:
1.
4. The method for preparing fluorocarbon / hydrocarbon oleogel microspheres with multiple structural configurations according to claim 1, characterized in that: Step (S2) includes the following sub-steps: (S2-1) Under room temperature and nitrogen protection, 4-dimethylaminopyridine was slowly added to a stirred suspension of 1H,1H-pentadecafluorooctanol in toluene. After stirring and mixing, terephthaloyl chloride and triethylamine were added in sequence, and the mixture was heated to 100°C and refluxed. (S2-2) After the reaction is completed, the reaction solution is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, the residue is dissolved in dichloromethane and washed with water several times; the organic phase is dried over anhydrous sodium sulfate and concentrated, and the crude product is purified by silica gel column chromatography to obtain a white solid compound, diperfluorohexyl ethyl terephthalate.
5. The method for preparing fluorocarbon / hydrocarbon oleogel microspheres with multiple structural configurations according to claim 4, characterized in that: In step (S2-1), the stirring time is 10 minutes; the heating reflux time is 48 hours; in step (S2-2), the eluent for silica gel column chromatography is n-hexane and dichloromethane in a volume ratio of 3:
1.
6. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to any one of claims 1-5, characterized in that: The hydrocarbon gelling solvent is selected from n-pentane, n-hexane, n-heptane, or n-octane; the fluorocarbon compound gelling solvent is selected from perfluorinated mixture FC-770, ethyl perfluorobutyl ether, or perfluorooctane; the surfactant is selected from Tween 20, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, DuPont FS-30, or sodium dodecyl sulfate.
7. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to any one of claims 1-5, characterized in that: The heating temperature in steps (S3) and (S4) is 80~95℃, and the mixing method is to gently shake or use a rotor as a stirrer with a speed of 50-100 rpm.
8. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to any one of claims 1-5, characterized in that: In step (S3), the volume ratio of hydrocarbon gelling solvent to fluorocarbon gelling solvent is 1:(0.1-10); the 2,5-pyridinedicarboxylic acid di(hexadecyl) ester gelling agent accounts for 3-10 wt% of the hydrocarbon gelling solvent; and the diperfluorohexyl ethyl terephthalate gelling agent accounts for 10-20 wt% of the fluorocarbon gelling solvent.
9. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to any one of claims 1-5, characterized in that: In step (S4), the surfactant has a mass fraction of 0.5 to 10 wt% in the aqueous solution; the total volume ratio of hydrocarbon gelling solvent and fluorocarbon compound gelling solvent to the surfactant solution is 1:(1 to 10).
10. A method for preparing fluorocarbon / hydrocarbon oil gel microspheres with multiple structural configurations according to any one of claims 1-5, characterized in that: In step (S5), the settling time during the ice bath is 0.5h-10h.