Preparation method of ultrathin high-barrier stretchable film

Abstract

The application relates to a preparation method of an ultrathin high-barrier stretchable film, and belongs to the technical field of packaging films. The preparation method of the ultrathin high-barrier stretchable film comprises the following steps: S1, dissolving an elastomer in an organic solvent to prepare a precursor solution; S2, sucking the precursor solution and discharging the precursor solution to a liquid interface, a system formed by the precursor solution and the liquid interface satisfies a Harkins spreading coefficient S>0, and the precursor solution is spread on the liquid interface; and S3, volatilizing the organic solvent of the precursor solution spread on the liquid interface, so that high molecules in the precursor solution are self-assembled to form a film on the liquid interface. The packaging film with the advantages of ultrathin thickness, high barrier and stretchability can be obtained, and lossless peeling and transfer can be realized.

Description

Technical Field

[0001] This application relates to the field of encapsulation film technology, and in particular to a method for preparing an ultrathin, high-barrier, stretchable film. Background Technology

[0002] As flexible electronics technology moves from the laboratory to industrialization, high-performance flexible electronic devices based on organic semiconductors, liquid metals, and flexible conductive polymers are showing broad application prospects in cutting-edge fields such as wearable health monitoring, implantable medical devices, flexible displays and electronic skin, and soft robots. In recent years, flexible electronic devices have been accelerating their development towards high integration, miniaturization, and thinning. For example, the thickness of large-scale stretchable integrated circuits containing hundreds of thousands or even millions of transistors has been compressed to the micrometer level. To ensure that devices achieve conformal and seamless bonding on various complex dynamic heterogeneous surfaces (such as human skin, brain tissue, and irregularly curved photovoltaic modules) and minimize the foreign body sensation in the human body or tissue, the encapsulation layer must evolve towards ultra-thinning at the hundred-nanometer level. However, the core functional layers inside these devices are often highly susceptible to corrosion from water vapor and oxygen in the air or bodily fluids, leading to semiconductor polymer degradation, material electrochemical failure, or the formation of "charge traps" within the polymer, thereby severely deteriorating carrier mobility and shortening the device's service life. Therefore, in the field of flexible electronic packaging, how to balance the ultra-thinness, high barrier properties, and mechanical stretchability of thin films remains a key bottleneck restricting the development of the entire industry.

[0003] Currently, while traditional inorganic rigid packaging materials used in chip manufacturing (such as metal foil, inorganic glass, and ceramics) exhibit excellent water vapor permeability due to their dense atomic arrangement at the intrinsic scale, their inherent high Young's modulus and non-stretchable properties make them highly susceptible to brittle fracture under dynamic conditions of bending, torsion, or large strain tension, making them completely unsuitable for the mechanical compliance requirements of flexible electronics. To address the flexibility matching challenge, the industry has widely turned to the introduction of stretchable elastomers such as polydimethylsiloxane (PDMS) and polyurethane (PU). However, these conventional elastomers have relatively loosely packed micromolecular chains, high free volume space, and high intrinsic gas permeability, resulting in inherently poor water vapor barrier performance; at ultra-thin scales, their barrier performance degrades further. In practical applications, to compensate for their insufficient barrier performance, it is often necessary to increase the packaging layer thickness to hundreds of micrometers or even millimeters, which not only compromises the overall thinness and flexibility of the device but also limits the conformal bonding design of highly integrated microdevices.

[0004] To construct polymer films at the micro- and nanoscale, existing laboratory and industrial fabrication processes primarily rely on solution spin coating or solution blade coating. However, when the target film thickness is reduced to the nanoscale, these traditional fluidic film-forming processes based on rigid solid substrates encounter intrinsic physical limitations. Driven by solution surface tension and rapid solvent evaporation, the polymer solution is prone to hydrodynamic instability, leading to severe non-uniformity in the final film thickness and inducing numerous microscopic surface defects such as nanoscale pores on and within the film. These defects directly constitute "defect channels" for water molecules within the ultrafilm, significantly increasing the water vapor transmission rate (WVTR) and greatly deteriorating the film's barrier properties. This makes it difficult to achieve long-term, stable protection in practical flexible electronic devices, causing rapid device failure in humid or physiologically sensitive environments. Furthermore, due to the strong adhesion between the film and the substrate interface, deformation, cracking, or severe self-adhesion easily occur during peeling and transfer applications, making non-destructive peeling and transfer difficult. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the objective of this application is to provide a method for preparing an ultrathin, high-barrier, stretchable film. This method yields an encapsulation film that is ultrathin, high-barrier, and stretchable, and enables non-destructive peeling and transfer.

[0006] In a first aspect, embodiments of this application provide a method for preparing an ultrathin, high-barrier, stretchable film, comprising: S1, Dissolve the elastomer in an organic solvent to prepare a precursor solution; S2, the precursor solution is drawn out to the receiving liquid interface. The system of the precursor solution and the receiving liquid satisfies the Hutchins spreading coefficient S>0, so that the precursor solution spreads at the receiving liquid interface. S3, the organic solvent in the precursor solution to be spread on the receiving liquid interface evaporates, allowing the polymer in the precursor solution to self-assemble at the receiving liquid interface to form a thin film. This application employs a system of precursor solution and receiving liquid satisfying the Huggins spreading coefficient S>0, controlling the discharge of the precursor solution at the receiving liquid interface to allow the precursor solution to spontaneously spread and self-assemble into a continuous, dense, and pore-free self-supporting solid nanoscale film. The resulting film has uniform thickness and is defect-free, achieving ultrathin synergistic high barrier properties and stretchability. Simultaneously, using the receiving liquid as a non-adhesive fluid substrate reduces strong adhesion, enabling non-destructive peeling and transfer of the film.

[0007] In some embodiments of this application, the concentration of the precursor solution is 0.1 mg / mL to 150 mg / mL.

[0008] This application utilizes a precursor solution of appropriate concentration, which facilitates the rapid and uniform spreading and diffusion of the precursor solution at the interface of the receiving liquid, thereby forming a thin film with uniform thickness, continuity, density, and no pores or defects.

[0009] In some embodiments of this application, the elastomer includes at least one of styrene-isobutylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, high molecular weight polyisobutylene, and thermoplastic polyurethane elastomer.

[0010] This application uses a suitable elastomer to formulate a precursor solution, which can ensure that the system of the precursor solution and the receiving liquid satisfies the Huggins spreading coefficient S>0, so as to facilitate the self-spreading and diffusion of the precursor solution at the receiving liquid interface; and because the suitable elastomer has strong intrinsic water vapor barrier properties, it can help improve the barrier properties of the film.

[0011] In some embodiments of this application, the process of aspirating the precursor solution to the receiving liquid interface includes: after aspirating the precursor solution, vertically lowering the pipette tip and keeping the tip 0-1 cm away from the receiving liquid interface, and aspirating the solution to the receiving liquid interface at a rate of 100 μL / s-150 μL / s.

[0012] This application sets an appropriate distance between the suction tip that draws the precursor solution and the interface of the receiving liquid, and discharges it to the interface of the receiving liquid at an appropriate speed, so as to facilitate the rapid and uniform spread and diffusion of the precursor solution on the interface of the receiving liquid, thereby forming a thin film with uniform thickness, continuity, density and no pore defects.

[0013] In some embodiments of this application, the evaporation of the organic solvent in the precursor solution spread on the receiving liquid interface includes: ventilating at a speed that does not disturb the calmness of the liquid surface in a direction parallel to the liquid surface on the upper side of the receiving liquid interface, so as to evaporate the organic solvent in the precursor solution spread on the receiving liquid interface.

[0014] This application uses appropriate ventilation direction and speed to allow the organic solvent in the precursor solution spread on the receiving liquid interface to evaporate, avoiding strong airflow blowing directly onto the liquid surface and disrupting the calmness of the liquid surface, as well as avoiding breaking the isotropic balance of the film spreading from the center to the periphery, so as to facilitate the formation of a film with uniform thickness, continuity, density and no pore defects.

[0015] In some embodiments of this application, after the polymer in the precursor solution self-assembles into a thin film at the receiving liquid interface, the method further includes: S4, using a frame structure to apply the thin film formed by the self-assembly at the receiving liquid interface, removing it from the receiving liquid interface and drying it to obtain an ultrathin high-barrier stretchable film.

[0016] This application demonstrates that after the polymer in the precursor solution self-assembles into a thin film at the receiving liquid interface, a frame structure is used to apply and remove the self-assembled thin film from the receiving liquid interface, thereby achieving non-destructive peeling and transfer.

[0017] In some embodiments of this application, the precursor solution further includes liquid polymers and / or resin monomers.

[0018] This application allows for gradient adjustment of the film modulus according to actual needs by adding liquid polymers and / or resin monomers to the precursor solution.

[0019] In some embodiments of this application, the molecular weight of the liquid polymer is no greater than 3000; the resin monomer includes acrylate monomers or acrylamide monomers.

[0020] This application utilizes the addition of a liquid polymer with a molecular weight not exceeding 3000 to the precursor solution to achieve low modulus properties in the film, depending on actual needs; and the addition of acrylate monomers or acrylamide monomers to the precursor solution to achieve high modulus properties in the film, depending on actual needs.

[0021] In some embodiments of this application, the mass percentage of the liquid polymer in the solute of the precursor solution is 5% to 60%.

[0022] This application employs the addition of an appropriate amount of liquid polymer to the precursor solution to achieve low modulus properties in the film while ensuring a high-quality film.

[0023] In some embodiments of this application, the mass percentage of the resin monomer in the solute of the precursor solution is 1% to 50%.

[0024] This application employs the addition of an appropriate amount of resin monomer to the precursor solution to achieve high modulus properties in the film while ensuring a high-quality film.

[0025] In some embodiments of this application, the liquid polymer includes at least one of polyisobutylene, liquid polybutene, polydimethylsiloxane, polybutadiene, polyisoprene, and polyalphaolefin.

[0026] This application uses a suitable liquid polymer to achieve low modulus properties in the film while ensuring good quality.

[0027] In some embodiments of this application, the acrylate monomers include at least one of hexanediol dimethacrylate, ethylene glycol dimethacrylate, hexanediol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methyl methacrylate, isobornyl acrylate, and isobornyl methacrylate.

[0028] In some embodiments of this application, the acrylamide monomers include at least one of dimethylbisacrylamide and n-isopropylacrylamide.

[0029] This application employs the addition of suitable acrylate monomers and acrylamide monomers to the precursor solution to achieve high modulus properties in the film while ensuring good film quality.

[0030] In some embodiments of this application, when the precursor solution includes resin monomers, after the film formed by the self-assembly of the receiving liquid interface using a frame structure is applied, removed from the receiving liquid interface and dried, the process further includes: S5, curing the film to initiate an in-situ polymerization reaction.

[0031] This application improves the modulus of the film by initiating an in-situ polymerization reaction to cure the resin monomers. Attached Figure Description

[0032] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 This is a schematic flowchart illustrating a method for preparing an ultrathin, high-barrier, stretchable film according to Embodiment 1 of this application.

[0034] Figure 2 A macroscopic photograph of the thin film provided for Experimental Example 1 of this application.

[0035] Figure 3 The water vapor transmission rate results provided for Test Example 2 of this application are shown in the figure.

[0036] Figure 4 The water vapor transmission rate results provided for Test Example 3 of this application are shown in the figure.

[0037] Figure 5 The scanning electron microscope image provided for Test Example 4 of this application.

[0038] Figure 6 The atomic force microscope phase diagram provided for Experimental Example 5 of this application. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0040] Traditional stretchable elastomers suffer from a significant decrease in water vapor barrier performance at nanoscale thicknesses due to their large free volume. Furthermore, existing spin-coating or blade-coating processes are prone to introducing defects such as pores into the film layer due to hydrodynamic instability, which greatly deteriorates the barrier performance of the film. At the same time, the strong adhesion between the ultrathin film and the rigid substrate makes it difficult to achieve non-destructive peeling and transfer.

[0041] To address the technical challenge of simultaneously achieving high barrier properties, good stretchability, and non-destructive transfer in flexible electronic packaging films at nanometer-thickness levels, this application provides a method for preparing an ultrathin, high-barrier, stretchable film, comprising: S1, the elastomer is dissolved in an organic solvent to prepare a precursor solution.

[0042] In some embodiments of this application, the organic solvent includes at least one of toluene, n-hexane, and cyclohexane. The system of precursor solution and receiving liquid can satisfy the Hutchins spreading factor S>0 by selecting different organic solvents or mixed solvents of the above-mentioned different organic solvents in different proportions.

[0043] In some embodiments of this application, trace amounts of small molecules such as aniline may be added to the precursor solution to adjust the surface tension of the precursor solution so that the system of the precursor solution and the receiving liquid satisfies the Huggins spreading coefficient S>0.

[0044] In some embodiments of this application, the concentration of the precursor solution is 0.1 mg / mL to 150 mg / mL. Further, the concentration of the precursor solution is 30 mg / mL to 150 mg / mL. As an example, the concentration of the precursor solution can be, but is not limited to, any value of 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, 100 mg / mL, 110 mg / mL, 120 mg / mL, 130 mg / mL, 140 mg / mL, or 150 mg / mL, or a range between these values. By using a precursor solution of suitable concentration, the precursor solution can spread and diffuse more rapidly and uniformly at the receiving liquid interface, thereby forming a thin film of uniform thickness, continuous, dense, and free of pores and defects. If the precursor solution concentration is too high and the solution viscosity is too high, the Marangoni flow at the gas-liquid interface will be hindered, making it difficult to diffuse rapidly and uniformly to the surroundings. This can easily lead to uneven film thickness or localized deposition defects.

[0045] In some embodiments of this application, the elastomer includes at least one of styrene-isobutylene-styrene block copolymer (SIBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), high molecular weight polyisobutylene (HMW-PIB), and thermoplastic polyurethane elastomer (TPU). By using a suitable elastomer to formulate the precursor solution, the system of the precursor solution and the receiving liquid can satisfy the Huggins spreading coefficient S>0, which facilitates the self-spreading and diffusion of the precursor solution at the receiving liquid interface; furthermore, because the intrinsic water vapor barrier properties of the suitable elastomer are strong, the barrier properties of the film can be improved.

[0046] In some embodiments of this application, the precursor solution further includes a liquid polymer and / or resin monomer. By adding liquid polymer and / or resin monomer to the precursor solution, the modulus of the film can be gradually adjusted according to actual needs.

[0047] Specifically, the precursor solution also includes liquid polymers or resin monomers.

[0048] In some embodiments of this application, the molecular weight of the liquid polymer is no greater than 3000; the resin monomer includes acrylate monomers or acrylamide monomers. By adding a liquid polymer with a molecular weight of no more than 3000 to the precursor solution, the film can obtain low modulus properties according to actual needs; by adding acrylate monomers or acrylamide monomers to the precursor solution, the film can obtain high modulus properties according to actual needs.

[0049] In some embodiments of this application, the mass percentage of the liquid polymer in the solute of the precursor solution is 5% to 60%. As an example, the mass percentage of the liquid polymer in the solute of the precursor solution can be, but is not limited to, any value of 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%, or a range between these values. By adding an appropriate amount of liquid polymer to the precursor solution, a low-modulus characteristic is achieved in the film while ensuring a good film quality.

[0050] In some embodiments of this application, the mass percentage of the resin monomer in the solute of the precursor solution is 1% to 50%. As an example, the mass percentage of the resin monomer in the solute of the precursor solution can be, but is not limited to, any value of 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, or a range between these values. By adding an appropriate amount of resin monomer to the precursor solution, high modulus properties are achieved in the film while ensuring a good film quality.

[0051] In some embodiments of this application, the liquid polymer includes at least one of polyisobutylene (PIB), liquid polybutene (PB), polydimethylsiloxane (PDMS), polybutadiene (LPBd), polyisoprene (LIR), and polyalphaolefin (PAO). By using a suitable liquid polymer, a low-modulus characteristic is achieved while ensuring a high-quality film. Based on the principle of compatibility of similar components, low-molecular-weight liquid polymers can selectively swell and enter the flexible midsection of the aforementioned elastomer, exhibiting excellent thermodynamic compatibility. The small molecules of the liquid polymer act as plasticizers in the polymer network, significantly increasing the free volume of the system. By continuously controlling the blending ratio of the elastomer and the liquid polymer, a gradient reduction in the mechanical modulus of the composite film can be achieved, making the film more flexible and precisely matching the extremely low modulus characteristics of biological soft tissue, reducing the foreign body sensation during adhesion. It should be noted that other low-molecular-weight liquid polymers that are compatible with the aforementioned elastomers and do not disrupt the interfacial hydrodynamic spreading stability can also be used.

[0052] In some embodiments of this application, the acrylate monomers include at least one selected from the following: hexanediol dimethacrylate (HDDMA), ethylene glycol dimethacrylate (EGDMA), hexanediol diacrylate (HDDA), diethylene glycol dimethacrylate (DEGDMA), neopentyl glycol diacrylate (NPGDA), ethylene glycol diacrylate (EGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol hexaacrylate (DPHA), methyl methacrylate (MMA), isobornyl acrylate (IBOA), and isobornyl methacrylate (IBOMA). In some embodiments of this application, the acrylamide monomers include at least one selected from the following: dimethylbisacrylamide (DMBAA) and n-isopropylacrylamide (NIPAM). By adding suitable acrylate monomers and acrylamide monomers to the precursor solution, high modulus properties of the film are achieved while ensuring a high-quality film. Acrylic ester monomers or acrylamide monomers crosslink within the elastomer matrix to construct a solid resin network, thereby increasing the modulus of the composite film. It should be noted that other resin monomer materials that can undergo in-situ polymerization through initiation reactions and, after curing, can also increase the film modulus.

[0053] S2, the precursor solution is drawn out to the receiving liquid interface. The system of precursor solution and receiving liquid satisfies the Hutchins spreading coefficient S>0, so that the precursor solution spreads at the receiving liquid interface. It should be noted that the formula for calculating the Huggins spread factor is: ;in, S -Hutchins spread coefficient; γ 承接液体 - Surface tension of the liquid; γ 前驱体溶液 - Surface tension of the precursor solution; γ 界面 - To bear the interfacial tension between the liquid and the precursor solution.

[0054] It should be noted that an optical contact angle / interfacial tension meter can be used for measurement. The surface tensions of the receiving liquid and precursor solution relative to air can be measured using the pendant drop method, Wilhelmy plate method, or ring method. The liquid-liquid interfacial tension between the receiving liquid and the precursor solution can be measured using the pendant drop method, reverse pendant drop method, or swirl drop method. These values ​​are then substituted into the above formula to calculate the Huggins spreading coefficient S. In actual process screening, whether stable spontaneous spreading occurs after the precursor solution is added to the receiving liquid interface can also be used as a qualitative criterion for determining whether the system has a positive spreading trend, without the need for quantitative determination of the magnitude of each surface tension.

[0055] In some embodiments of this application, the temperature of the precursor solution and the temperature of the receiving liquid can be controlled so that the system of the precursor solution and the receiving liquid satisfies the Huggins spreading factor S>0.

[0056] In some embodiments of this application, the aspiration of the precursor solution to the receiving liquid interface includes: after aspirating the precursor solution, holding the pipette tip vertically downwards with the tip 0-1 cm from the receiving liquid interface, and aspirating at a rate of 100 μL / s-150 μL / s to the receiving liquid interface. As an example, the distance between the tip and the receiving liquid interface can be, but is not limited to, any value from 0, 0.1 cm, 0.2 cm, 0.3 cm, 0.4 cm, 0.5 cm, 0.6 cm, 0.7 cm, 0.8 cm, 0.9 cm, or 1 cm, or a range between these values. The aspiration rate can be, but is not limited to, any value from 100 μL / s, 110 μL / s, 120 μL / s, 130 μL / s, 140 μL / s, or 150 μL / s, or a range between these values. By setting an appropriate distance between the pipette tip that draws the precursor solution and the interface of the receiving liquid, and by discharging the solution at an appropriate rate towards the interface, the precursor solution can be rapidly and uniformly spread and diffused at the interface, forming a thin film of uniform thickness, continuity, density, and free of pores and defects. Specifically, a pipette is used to draw the precursor solution. If the pipette tip is too high above the receiving liquid interface, or if the force applied during the dispensing is too great, the precursor solution may break through the surface tension barrier of the receiving liquid due to excessive initial kinetic energy, forming free droplets below the water surface. These droplets then rise and break in specific areas, resulting in an excessive amount of precursor solution in those areas and insufficient amount in others, ultimately affecting the film formation. If the drop speed is too slow (falling in slow, discontinuous droplets), the precursor solution that first falls to the water surface may experience rapid solvent evaporation, or even premature solidification of the outer layer, causing a surge in local viscosity. This prevents subsequent drops of precursor solution from achieving uniform fluid fusion, leading to the formation of defective films with uneven surface thickness.

[0057] In some embodiments of this application, instruments with high-precision flow and height feedback controllers can be used in automated production lines to achieve precise control of the precursor solution being discharged to the receiving liquid interface.

[0058] Specifically, the receiving liquid is water. As an example, for ultra-thin films, ultrapure water is selected as the receiving liquid, which can provide a higher intrinsic surface tension than ordinary pure water, thereby directly increasing the spreading coefficient S and providing a stronger thermodynamic spreading driving force for the precursor solution; for films that do not require ultra-thin thickness, the receiving liquid can be replaced with deionized water or ordinary tap water.

[0059] In some embodiments of this application, KOH, K2SO4, etc. can be added to the ultrapure water receiving the liquid to further increase the surface tension of the aqueous phase, thereby improving the interfacial spreading performance.

[0060] In some embodiments of this application, a clean, circular container is used to hold the receiving liquid. After the precursor solution is dripped into the center, its diffusion rate to the surrounding gas-liquid interface is isotropic in terms of hydrodynamics. The physical boundary of the circular container can maintain the symmetry of fluid diffusion and the uniformity of the final film thickness to the greatest extent. In addition, after injecting the receiving liquid into the circular container, it is allowed to stand until the receiving liquid is completely calm to control the hydrodynamics. This avoids the precursor solution being added before the water is completely calm or before the water is fully settled. If the precursor solution is added before the water is fully calm, it will rotate with the water flow, resulting in a rotating boundary on the macroscopic surface of the final film, which would disrupt the overall continuity of the film.

[0061] S3 evaporates the organic solvent in the precursor solution spread on the receiving liquid interface, allowing the polymer in the precursor solution to self-assemble into a thin film at the receiving liquid interface.

[0062] In some embodiments of this application, the evaporation of the organic solvent in the precursor solution spread on the receiving liquid interface includes: ventilating at a speed that does not disturb the calmness of the liquid surface in a direction parallel to the liquid surface on the upper side of the receiving liquid interface, so as to evaporate the organic solvent in the precursor solution spread on the receiving liquid interface. Specifically, the ventilation speed is no greater than 1 m / s. By using appropriate ventilation direction and speed to evaporate the organic solvent in the precursor solution spread on the receiving liquid interface, strong airflow is avoided from directly blowing onto the liquid surface and disrupting the calmness of the liquid surface, and the isotropic balance of the film diffusion from the center to the periphery is also avoided, which is conducive to the formation of a film with uniform thickness, continuity, density and no pore defects. If the ventilation speed is too high, the strong airflow will not only disrupt the physical calmness of the water surface, causing the polymer liquid film to be subjected to non-uniform in-plane shear force during the spreading and evaporation molding stages, inducing macroscopic surface wrinkles, but will also disrupt the isotropic balance of the film diffusion from the center to the periphery, resulting in uneven thickness of the finally cured film, and even the appearance of rotation-induced cracks.

[0063] It should be noted that organic solvents such as toluene are generally toxic, and the organic solvents in the precursor solution spread at the receiving liquid interface need to be volatilized in a fume hood.

[0064] In some embodiments of this application, perforated tin foil can be placed over the container holding the liquid, or a semi-enclosed evaporation hood with micropores can be installed to control the local solvent vapor pressure, concentration gradient, and evaporation rate, thereby further improving the stability of the organic solvent evaporation environment.

[0065] In some embodiments of this application, after the polymer in the precursor solution self-assembles into a thin film at the receiving liquid interface, the method further includes: S4, using a frame structure to apply and remove the self-assembled thin film from the receiving liquid interface and then drying it to obtain an ultrathin, high-barrier, stretchable thin film. After the polymer in the precursor solution self-assembles into a thin film at the receiving liquid interface, non-destructive peeling and transfer can be achieved by using a frame structure to apply and remove the self-assembled thin film from the receiving liquid interface.

[0066] In some embodiments of this application, the film is applied to the liquid receiving interface in two ways: (1) from bottom to top: the frame structure is submerged underwater from the edge of the container holding the liquid, and then moved horizontally to directly below the suspended film. The liquid is then pulled up at a certain angle and at a constant speed; (2) from top to bottom: the frame structure is held parallel to the liquid receiving interface film from top to bottom, so that the film adheres to the frame structure. The free edges of the film are folded over and applied to the side of the frame structure, and then the film is removed from the water surface at an angle.

[0067] In some embodiments of this application, adhesive tape or mechanical clamps can be applied around the perimeter of the frame structure. When removing the film for testing, the ultrathin films at the hundred-nanometer scale are prone to rapid shrinkage after being completely detached from a rigid or fluid-supported substrate, leading to irreversible and severe self-adhesion. By applying adhesive tape or fixing mechanical clamps around the frame structure, uniform in-plane tension can be applied to the suspended ultrathin film, forcibly maintaining its flat and spreadable state. This provides structural support for the subsequent complete removal of the film from the frame and conformal seamless bonding to target devices or biological soft tissues.

[0068] In some embodiments of this application, the frame structure can be a rigid metal frame, a polymer material frame (such as PET or PI), a ceramic frame, or a composite material frame.

[0069] In some embodiments of this application, the receiving liquid needs to be replaced after the film is retrieved. The cleanliness of the aqueous phase of the receiving liquid plays a decisive role in the film formation quality. Even trace amounts of grease or dust contamination can significantly reduce the surface tension of the aqueous phase, preventing the precursor solution from effectively spreading on the water surface. Therefore, the receiving liquid must be replaced after film retrieval to maintain interface purity. Furthermore, for the needs of large-area continuous industrial preparation, the circular static container holding the receiving liquid can be replaced with an automated film retrieval tool with a control system to avoid introducing impurities into the aqueous phase by hand during the film retrieval process.

[0070] In some embodiments of this application, before drying the film that has been applied and removed from the liquid interface, the frame structure can be rinsed with anhydrous ethanol, allowing the ethanol to flow naturally through the film and remove surface moisture for quick drying.

[0071] In some embodiments of this application, when the precursor solution includes resin monomers, after the film formed by the self-assembly of the receiving liquid interface using a frame structure is applied, removed from the receiving liquid interface, and dried, the method further includes: S5, curing the film by in-situ polymerization. By curing the film by in-situ polymerization, the resin monomers undergo in-situ polymerization and curing, cross-linking and constructing a solid resin network within the elastomer matrix to improve the modulus of the film.

[0072] In some embodiments of this application, curing the in-situ polymerization reaction initiated by the thin film includes at least one of ultraviolet light initiation, thermal initiation, and plasma initiation.

[0073] In some embodiments of this application, when using ultraviolet light initiation, a free radical photoinitiator needs to be added to the precursor solution, and the film is irradiated with ultraviolet light (UV) for 15 min to 20 min.

[0074] In some embodiments of this application, the free radical photoinitiator includes a first free radical photoinitiator and a second free radical photoinitiator. The first free radical photoinitiator includes at least one of 2,2-diethoxyacetophenone (DEAP), 1-hydroxycyclohexylphenyl ketone (photoinitiator 184), 2-hydroxy-2-methylpropionylphenyl (photoinitiator 1173), 2,2-dimethoxy-2-phenylacetophenone (photoinitiator 651), and 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (photoinitiator 907). The second radical photoinitiator includes at least one of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819 / BAPO), ethyl 2,4,6-trimethylbenzoyl phenylphosphonate (photoinitiator TPO-L), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. It should be noted that the first radical photoinitiator can also be other non-yellowing or low-yellowing Type I α-hydroxy ketone or acetophenone derivatives. The second radical photoinitiator can also be other acylphosphine oxide (APO / BAPO) compounds with high absorption efficiency in the long-wavelength or near-visible light region. The first free radical photoinitiator is mainly responsible for absorbing short-wave UV light, overcoming surface oxygen inhibition, and ensuring the dryness of the film surface (surface curing); while the second free radical photoinitiator is responsible for absorbing long-wave UV light (such as 365 nm~405 nm), using its "photobleaching" effect to allow light to penetrate to the bottom of the film, ensuring the complete curing of the entire film (deep curing).

[0075] In some embodiments of this application, the mass percentage of the resin monomer, the first free radical photoinitiator, and the second free radical photoinitiator in the solute of the precursor solution is 1% to 50%. Further, the mass percentage of the resin monomer, the first free radical photoinitiator, and the second free radical photoinitiator in the solute of the precursor solution is 5% to 25%. As an example, the mass percentage of the resin monomer, the first free radical photoinitiator, and the second free radical photoinitiator in the solute of the precursor solution can be, but is not limited to, any value of 5%, 10%, 15%, 20%, or 25%, or a range between both.

[0076] In some embodiments of this application, the mass ratio of resin monomer, first free radical photoinitiator and second free radical photoinitiator is 96~98 : 1~2 : 1~2.

[0077] In some embodiments of this application, when ultraviolet light is used for initiation, selective exposure can be performed by placing a photomask with a transparent pattern on top of the thin film. This allows only the transparent areas to undergo in-situ polymerization and curing, while the opaque areas maintain their original low modulus. This enables the patterned distribution of spatial modulus within a single-layer ultrathin film.

[0078] This application employs a system of precursor solution and receiving liquid satisfying the Huggins spreading coefficient S>0, controlling the discharge of the precursor solution at the receiving liquid interface to allow the precursor solution to spontaneously spread and self-assemble into a continuous, dense, and pore-free self-supporting solid nanoscale film. The resulting film has uniform thickness and is defect-free, achieving ultrathin synergistic high barrier properties and stretchability. Simultaneously, using the receiving liquid as a non-adhesive fluid substrate reduces strong adhesion, enabling non-destructive peeling and transfer of the film.

[0079] The features and performance of this application will be further described in detail below with reference to the embodiments.

[0080] The materials used in the embodiments of this application are as follows: 1. Polystyrene-polyisobutylene-polystyrene (SIBS, SIBSTAR-102T), purchased from Kaneka Corporation, with a polystyrene content of 15 wt%.

[0081] 2. Toluene (AR), purchased from Shanghai Lingfeng.

[0082] 3. Polyisobutylene (PIB, Mn 400), manufactured by Daelim, South Korea.

[0083] 4.1, 6-Hexanediol dimethacrylate (HDDMA), purchased from Bid Pharmaceuticals.

[0084] 5.2,2-Diethoxyacetophenone (DEAP), purchased from Bid Pharmaceuticals.

[0085] 6,2,4,6-Trimethylbenzoyl diphenylphosphine oxide (TPO), purchased from Maclean's.

[0086] 7. Styrene-ethylene-butene-styrene block copolymer (SEBS-H1041), purchased from Asahi Kasei Corporation, Japan.

[0087] 8. Polydimethylsiloxane (PDMS), purchased from Dow Corning, DC184, with a prepolymer:curing agent ratio of 10:1.

[0088] Example 1 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film, including: S1, Dissolve SIBS in toluene and stir continuously at room temperature until completely dissolved to prepare a pure SIBS precursor solution with a concentration of 150 mg / mL; S2, take a circular glass container with a diameter of 21 cm, fill it with ultrapure water, and let it stand until the aqueous phase is completely calm; use a pipette to draw 300 μL of the above pure SIBS precursor solution, place the pipette tip vertically downward close to the center surface of the aqueous phase by 0.5 cm, and slowly press it out at a uniform speed of 100 μL / s without breaking the gas-liquid interface, so that the solution flows into the water surface in a continuous bundle and spreads in all directions, so that the pure SIBS precursor solution spreads on the water surface; S3, the pure SIBS precursor solution spread on the water surface is placed in a fume hood and ventilated at a speed of 0.5 m / s in a direction parallel to the water surface above the water surface, until the toluene completely evaporates and forms a solid film. S4. Hold the metal frame parallel to the water surface from top to bottom, so that the film adheres to the edge of the metal frame. At the same time, fold the free edges of the film around the edges and attach them to the side of the metal frame. Remove the film from the water surface at an angle. After removing it from the aqueous phase, carefully rinse it with ethanol and dry it to obtain a pure SIBS encapsulation film.

[0089] Example 2 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film, including: S1, SIBS and PIB with a molecular weight of 400 are dissolved in toluene and stirred continuously at room temperature until completely dissolved to prepare a precursor solution with a total concentration of 150 mg / mL. The mass percentage of PIB in the solute of the precursor solution is 30%. S2, take a circular glass container with a diameter of 21 cm, fill it with ultrapure water, and let it stand until the aqueous phase is completely calm; use a pipette to draw 400 μL of the above precursor solution, place the pipette tip vertically downward close to the center surface of the aqueous phase by 0.5 cm, and slowly press it out at a uniform speed of 100 μL / s without breaking the gas-liquid interface, so that the solution flows into the water surface in a continuous bundle and spreads in all directions, so that the precursor solution spreads on the water surface; S3, the precursor solution spread on the water surface is placed in a fume hood and ventilated at a speed of 0.5 m / s in a direction parallel to the water surface above the water surface, until the toluene completely evaporates and forms a solid film. S4. Hold the metal frame parallel to the water surface from top to bottom, so that the film adheres to the edge of the metal frame. At the same time, fold the free edges of the film around the perimeter and attach them to the side of the metal frame. Remove the film from the water surface at an angle. After removing it from the aqueous phase, rinse it with ethanol, allowing the ethanol to flow naturally through the film to avoid breaking it. Then dry it to obtain a low-modulus encapsulation film.

[0090] Example 3 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 2 is that the mass percentage of PIB in the solute of the precursor solution is 25%.

[0091] Example 4 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 2 is that the mass percentage of PIB in the solute of the precursor solution is 20%.

[0092] Example 5 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 2 is that the mass percentage of PIB in the solute of the precursor solution is 15%.

[0093] Example 6 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 2 is that the mass percentage of PIB in the solute of the precursor solution is 10%.

[0094] Example 7 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 2 is that the mass percentage of PIB in the solute of the precursor solution is 5%.

[0095] Example 8 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film, including: S1, SIBS, HDDMA, DEAP, and TPO are dissolved in toluene and stirred continuously at room temperature until completely dissolved to prepare a precursor solution with a concentration of 150 mg / mL. The mass percentage of HDDMA, DEAP, and TPO in the solute of the precursor solution is 25%; the mass ratio of HDDMA to DEAP and TPO is 98:1:1. S2, take a circular glass container with a diameter of 21 cm, fill it with ultrapure water, and let it stand until the aqueous phase is completely calm; use a pipette to draw 300 μL of the above precursor solution, place the pipette tip vertically downward close to the center surface of the aqueous phase by 0.5 cm, and slowly press it out at a uniform speed of 100 μL / s without breaking the gas-liquid interface, so that the solution flows into the water surface in a continuous bundle and spreads in all directions, so that the precursor solution spreads on the water surface; S3, the precursor solution spread on the water surface is placed in a fume hood and ventilated at a speed of 0.5 m / s in a direction parallel to the water surface above the water surface, until the toluene completely evaporates and forms a solid film. S4. Hold the metal frame parallel to the water surface from top to bottom, so that the film adheres to the edge of the metal frame. At the same time, fold the free edges of the film around the edges and attach them to the side of the metal frame. Remove the film from the water surface at an angle. After removing it from the aqueous phase, rinse it with ethanol, allowing the ethanol to flow naturally through the film to avoid breaking it. Then dry it and expose it with ultraviolet light with a wavelength of 365nm for 15 minutes to cure the HDDMA and obtain a high modulus encapsulation film.

[0096] Example 9 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Example 8 is that the mass percentage of HDDMA, DEAP, and TPO in the solute of the precursor solution is 20%.

[0097] Example 10 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 8 is that the mass percentage of HDDMA, DEAP, and TPO in the solute of the precursor solution is 15%.

[0098] Example 11 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 8 is that the mass percentage of HDDMA, DEAP, and TPO in the solute of the precursor solution is 10%.

[0099] Example 12 This embodiment provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Embodiment 8 is that the mass percentage of HDDMA, DEAP, and TPO in the solute of the precursor solution is 5%.

[0100] Comparative Example 1 This comparative example provides a method for preparing an ultrathin, high-barrier, stretchable film, comprising: S1, Dissolve SIBS in toluene and stir continuously at room temperature until completely dissolved to prepare a pure SIBS precursor solution with a concentration of 150 mg / mL; S2. On a flat glass substrate that has been plasma cleaned, a 10 wt% glucose solution is first dropped onto it and then spin-coated at 2000 rpm for 30 s using a spin coater to form a glucose sacrificial layer. S3, place in a 50 °C oven to dry for 10 min, then add the above pure SIBS precursor solution dropwise, and spin coat at 2000 rpm for 30 s using a spin coater; S4, then placed in a 50 °C oven for 1 h to completely evaporate the solvent. After taking it out, transparent tape was attached to the four sides of the film to fix it. Then it was placed in water. After the glucose sacrificial layer dissolved, the film fixed by the tape separated from the glass substrate, and a pure SIBS encapsulation film was obtained.

[0101] Comparative Example 2 This comparative example provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Comparative Example 1 is that SIBS is replaced with styrene-ethylene-butene-styrene block copolymer (SEBS).

[0102] Comparative Example 3 This comparative example provides a method for preparing an ultrathin, high-barrier, stretchable film. The difference from Comparative Example 1 is that SIBS is replaced with polydimethylsiloxane (PDMS), the PDMS prepolymer and curing agent are mixed at a mass ratio of 10:1 and then diluted with n-hexane to obtain a PDMS precursor solution with a total concentration of 25wt%. In step S3, after spin coating, the film is placed in an 80 °C oven for 2 h to allow the PDMS to fully crosslink.

[0103] Experimental Example 1 This experimental example compares the macroscopic photographs taken of the thin films prepared by the methods provided in Example 1 and Comparative Example 1. The results are as follows: Figure 2 As shown.

[0104] Depend on Figure 2 The results show that, Figure 2 As shown in (b), the thin film prepared by spin coating in Comparative Example 1 exhibits significant thickness unevenness and linear defects on the surface due to hydrodynamic instability caused by the rapid evaporation of solvent during spin coating, as revealed by the interference pattern. In contrast, as... Figure 2As shown in (a), the thin film prepared by the method provided in Example 1 has a smooth surface, highly uniform thickness, and exhibits a defect-free, large-area continuous physical morphology. This application demonstrates that by employing a system of precursor solution and receiving liquid satisfying the Huggins spreading coefficient S>0, the precursor solution is controlled to drain at the receiving liquid interface, allowing the precursor solution to spontaneously spread and self-assemble at the receiving liquid interface to form a continuous, dense, and pore-free self-supporting solid nanoscale thin film. The resulting film has uniform thickness and is defect-free, achieving ultrathin synergistic high barrier properties and stretchability.

[0105] Experimental Example 2 This experimental example tests the water vapor transmission rate (WVTR) of the films prepared by the methods provided in Example 1 and Comparative Examples 1-3, as follows: Fill a 20 mL sample vial with anhydrous copper sulfate to approximately 3 / 4 full, seal it with the test film, and then seal the threaded connection between the film and the vial opening with UV-curable adhesive. Cure under UV light, weigh the vial, and record the weight. Then, immerse the vial in water slightly above the film at the opening, recording the immersion time. After approximately 14 days, remove the vial and record the time after removal to calculate the immersion duration. Rinse the vial surface with anhydrous ethanol and allow it to air dry. Once completely dry, weigh the vial again and record the weight, calculating the mass difference. Divide the mass difference (g) by the immersion time (days), and then by the vial opening area (square meters) to obtain the WVTR data. Results are as follows: Figure 3 As shown.

[0106] Depend on Figure 3 The results show that the film prepared by the method provided in Example 1 has a WVTR value of only 72.8g. m -2 day -1 This demonstrates superior water vapor barrier properties. The WVTR value of the film prepared by spin coating in Comparative Example 1 reaches 440.0 g. m -2 day -1 Comparative Example 2 shows that the WVTR value of the film prepared using the conventional elastomer SEBS reaches 597.1 g. m -2 day -1 In Comparative Example 3, the film prepared using the conventional elastomer PDMS achieved a WVTR value of 1469.8 g. m -2 day -1The thin film prepared by the method provided in Example 1 has a WVTR value that is several times or even an order of magnitude lower than that of the thin films prepared by the methods provided in Comparative Examples 1-3, achieving a synergy between ultra-thin thickness and high barrier performance. This application utilizes a system of precursor solution and receiving liquid satisfying the Huggins spreading coefficient S>0, and employs an elastomer with high intrinsic water vapor barrier capability to control the discharge of the precursor solution at the receiving liquid interface. This allows the precursor solution to spontaneously spread and self-assemble at the receiving liquid interface, forming a continuous, dense, and pore-free self-supporting solid nanoscale thin film. The resulting film has uniform thickness and is defect-free, achieving ultra-thin synergistic high barrier and stretchability.

[0107] Experimental Example 3 This experimental example tested the water vapor transmission rate (WVTR) of the films prepared by the methods provided in Examples 1-12, and the results are as follows: Figure 4 As shown.

[0108] Depend on Figure 4 The results show that by introducing different proportions of PIB or cured resin into the SIBS precursor to achieve modulus gradient control, the modified film maintains excellent water vapor barrier performance comparable to that of pure SIBS film while achieving significant modulus matching. The barrier performance did not decrease significantly due to changes in composition. This demonstrates that by adding appropriate amounts of liquid polymers or resin monomers to the precursor solution, the modulus of the film can be gradient-adjusted according to actual needs without altering its excellent water vapor barrier performance.

[0109] Test Example 4 This experimental example uses scanning electron microscopy (SEM) to examine the microstructure of the thin film prepared by the method provided in Example 1. The results are as follows: Figure 5 As shown.

[0110] Depend on Figure 5 The results show that the film prepared by the method provided in Example 1 has an extremely smooth and continuous surface, and no micropores or cracks caused by hydrodynamic instability were observed, confirming the high density of the film at the nanoscale. This application demonstrates that by employing a system of precursor solution and receiving liquid satisfying the Huggins spreading coefficient S>0, and controlling the discharge of the precursor solution at the receiving liquid interface, the precursor solution spontaneously spreads and self-assembles at the receiving liquid interface to form a continuous, dense, and pore-free self-supporting solid nanoscale film. The resulting film has uniform thickness and is defect-free, achieving ultrathin synergistic high barrier properties and stretchability.

[0111] Experimental Example 5 In this experimental example, the microstructure of the thin films prepared by the methods provided in Example 1 and Comparative Example 1 was examined using atomic force microscopy (AFM). The results are as follows: Figure 6 As shown.

[0112] Depend on Figure 6 The results show that the film prepared by the method provided in Example 1 exhibits highly ordered horizontal microphase separation of SIBS molecules within a quasi-two-dimensional plane due to the constraint of the extremely high initial interfacial energy of the ultrapure water phase. This results in a dense nanoscale network structure formed by the hard polystyrene (PS) segments and the flexible PIB segments. This unique horizontal microphase separation fundamentally blocks vertical defect channels penetrating the film thickness direction, significantly extending the diffusion path of water molecules within the film and providing microstructural support for ultra-high water vapor barrier at the ultimate thickness. In contrast, the film prepared by spin coating in Comparative Example 1 exhibits larger porosity defects.

[0113] The embodiments described above are some, but not all, of the embodiments of this application. The detailed description of the embodiments of this application is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

Claims

1. A method for preparing an ultrathin, high-barrier, stretchable film, characterized in that, include: S1, Dissolve the elastomer in an organic solvent to prepare a precursor solution; S2, the precursor solution is drawn out to the receiving liquid interface, and the system of the precursor solution and the receiving liquid satisfies the Hutchins spreading coefficient S>0, so that the precursor solution spreads at the receiving liquid interface; S3, the organic solvent of the precursor solution spread on the receiving liquid interface is evaporated, so that the polymer in the precursor solution self-assembles to form a thin film at the receiving liquid interface.

2. The preparation method according to claim 1, characterized in that, The concentration of the precursor solution is 0.1 mg / mL to 150 mg / mL.

3. The preparation method according to claim 2, characterized in that, The elastomer includes at least one of styrene-isobutylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, high molecular weight polyisobutylene, and thermoplastic polyurethane elastomer.

4. The preparation method according to claim 1, characterized in that, The step of aspirating the precursor solution to the receiving liquid interface includes: after aspirating the precursor solution, vertically pointing the pipette tip downwards and keeping the tip 0-1 cm away from the receiving liquid interface, and aspirating the solution to the receiving liquid interface at a rate of 100 μL / s-150 μL / s.

5. The preparation method according to claim 1, characterized in that, The process of evaporating the organic solvent of the precursor solution spread on the receiving liquid interface includes: ventilating at a speed that does not disturb the calmness of the liquid surface in a direction parallel to the liquid surface on the upper side of the receiving liquid interface, so as to evaporate the organic solvent of the precursor solution spread on the receiving liquid interface.

6. The preparation method according to claim 1, characterized in that, After the polymer in the precursor solution self-assembles into a thin film at the receiving liquid interface, the method further includes: S4, applying the thin film formed by the self-assembly at the receiving liquid interface using a frame structure, removing it from the receiving liquid interface, and drying it to obtain an ultrathin high-barrier stretchable film.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The precursor solution further includes a liquid polymer and / or resin monomer; Optionally, the molecular weight of the liquid polymer is not greater than 3000; the resin monomer includes acrylate monomers or acrylamide monomers.

8. The preparation method according to claim 7, characterized in that, The liquid polymer comprises 5% to 60% by mass of the solute in the precursor solution; And / or, the resin monomer has a mass percentage of 1% to 50% in the solute of the precursor solution.

9. The preparation method according to claim 8, characterized in that, The liquid polymer includes at least one of polyisobutylene, liquid polybutene, polydimethylsiloxane, polybutadiene, polyisoprene, and polyalphaolefin. And / or, the acrylate monomers include at least one of the following: hexanediol dimethacrylate, ethylene glycol dimethacrylate, hexanediol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methyl methacrylate, isobornyl acrylate, and isobornyl methacrylate; And / or, the acrylamide monomers include at least one of dimethylbisacrylamide and n-isopropylacrylamide.

10. The preparation method according to claim 8, characterized in that, When the precursor solution includes resin monomers, after the film formed by self-assembly of the receiving liquid interface using a frame structure is applied, removed from the receiving liquid interface and dried, the process further includes: S5, curing the film by initiating an in-situ polymerization reaction.

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