Elastomer with nanometer-sized imprinting precision and method of production and use

Abstract

The present application relates to the field of high polymer nanomaterials, and particularly relates to an elastomer with nano-sized imprinting precision and a preparation method and application, a surface of the elastomer is an imprinting layer with nano-structure, the imprinting layer has imprinting structures with a minimum diameter of sub-10 nanometers and a length-diameter ratio of (3-100):1, a water contact angle of the imprinting layer is 70-140 DEG, the preparation method comprises synthesis of a dynamic unit, construction of a dynamic heterogeneous elastomer, nano-imprinting, introduction of a dynamic covalent bond and a crystalline phase into the dynamic heterogeneous elastomer, in the process of imprinting, the elastomer network enters nano-pores of a template and is fully filled, reassembled into a complete network structure, and the crystalline phase further limits resilience of the elastomer network to ensure fidelity of the imprinting structure, that is, the elastomer is prepared by translocation crystallization of the elastomer network in the nano-pores.

Description

Technical Field

[0001] This invention relates to the field of polymer nanomaterials, and more particularly to an elastomer with nanoscale imprinting precision, its preparation method, and its application. Background Technology

[0002] In nature, countless examples demonstrate the remarkable and superior properties resulting from the structuring of surfaces and interfaces, especially at the nanoscale, such as the self-cleaning properties of lotus leaves, the adhesive properties of gecko feet, and the drag-reducing function of shark skin. Elastomers, as one of the most promising functional soft materials, have attracted widespread attention and are applied in various fields. Therefore, the diversity and precision control of elastomer surface structures are crucial for enriching the functions of materials and further expanding their applications.

[0003] Nanoimprint lithography is an emerging photolithography technique that can be used to construct precise, high-throughput nanostructure patterns, with enormous application potential in electronics, optics, magnetic devices, and nanofluidics. In recent years, high-performance nanoimprint materials and structures have developed rapidly. However, current imprint materials mainly focus on thermoplastic polymers. For example, CN102336016B discloses a viscoelastic thermally triggered ultrasonic imprinting method for thermoplastic polymers. Its characteristic is that the mold is heated to 1-60°C above the glass transition temperature of the thermoplastic polymer, a polymer substrate is placed on the mold and subjected to ultrasonic vibration. Under the action of ultrasonic vibration, the polymer generates viscoelastic heat, softening the polymer in the forming area. Under pressure, it flows and fills the microstructure of the mold. Before applying ultrasonic vibration, heating the mold allows the polymer in the forming area to directly enter the viscoelastic heat generation stage, avoiding solid-solid contact in a high-hardness state at the polymer-mold interface. This minimizes vibration damage to the mold, effectively improving mold life and forming efficiency. However, the high-temperature and high-pressure requirements of this type of material also limit its practical application. For elastomer systems, spontaneous shape recovery driven by network entropy elasticity after demolding significantly hinders the stable fixation of the embossed structure.

[0004] Recent advances have focused on integrating shape memory properties into elastomers to suppress entropy recovery, thereby ensuring structural fidelity. However, current imprinted features on elastomer surfaces are still limited to the micrometer scale, making it difficult to achieve nanoscale imprinted structures.

[0005] Based on the above, there are pressing technical problems in the existing technology, such as how to simultaneously manufacture structures with nanoscale features and high aspect ratios on the surface of an elastomer. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure. The imprinted layer has an imprinted structure with a minimum diameter of sub-10 nm and an aspect ratio of (3-100):1. The aspect ratio is the ratio of the depth to the diameter of the imprinted structure. The water contact angle of the imprinted layer is 70-140°.

[0007] Furthermore, the diameter of the imprinted structure is from sub-10 nm to 300 nm.

[0008] The present invention also provides a method for preparing the above-mentioned elastomer with nanoscale imprinting precision, including the synthesis of dynamic units, the construction of dynamic heteroelastomers, and nanoimprinting;

[0009] Dynamic covalent bonds and crystalline phases are introduced into a dynamic heteroelastomer. During the imprinting process, the elastomer network enters the nanopores of the template and is fully filled, reassembling into a complete network structure. Furthermore, the crystalline phase further restricts the resilience of the elastomer network to ensure the fidelity of the imprinted structure. That is, the elastomer is prepared by metasomatic crystallization of the elastomer network in the nanopores.

[0010] Furthermore, the preparation method specifically includes the following steps: Step 1, Synthesis of dynamic unit: The dynamic monomer is dissolved in a solvent, an alkaline compound is added, the system temperature is lowered to 0℃, and then an acyl chloride compound is added dropwise. After the addition is complete, the reaction is stirred at room temperature. The reaction mixture was then filtered, washed, and dried to obtain the dynamic unit. Step 2, Construction of dynamic heteroelastomer: Dynamic units, propylene compounds, long-chain alkyl ester monomers and initiators are polymerized to obtain dynamic heteroelastomer; Step 3, Nanoimprinting: The dynamic heteroelastomer is nanoimprinted, cooled to room temperature after imprinting, and then etched in an alkaline solution to obtain an elastomer with nanoscale imprinting precision.

[0011] Furthermore, the dynamic monomer described in step 1 contains dynamic covalent bonds.

[0012] Furthermore, the dynamic monomer mentioned in step 1 includes one of the following: disulfide group, imine bond, hydrazone bond, Diels-Alder bond (bond generated by the Diels-Alder reaction), borate ester bond, and transester / urethane ester exchange bond.

[0013] Furthermore, the dynamic monomers containing disulfide groups include, but are not limited to, cystine and 2-hydroxyethyl disulfide.

[0014] Furthermore, the solvents mentioned in step 1 include, but are not limited to, alcohol solvents, haloalkanes solvents, or amide solvents.

[0015] Furthermore, the alcohol solvent includes, but is not limited to, methanol and ethanol.

[0016] Furthermore, the halogenated hydrocarbon solvent includes, but is not limited to, dichloromethane.

[0017] Furthermore, the amide solvents include, but are not limited to, N,N-dimethylformamide.

[0018] Furthermore, the alkaline compound mentioned in step 1 includes inorganic or organic bases.

[0019] Furthermore, the inorganic base includes, but is not limited to, sodium hydroxide and potassium hydroxide.

[0020] Furthermore, the organic base includes, but is not limited to, triethylamine.

[0021] Furthermore, the molar volume ratio of the dynamic monomer and solvent mentioned in step 1 is (10-30):(20-150), where moles are measured in mmol and volumes are measured in mL.

[0022] Further, the molar ratio of the dynamic monomer and the basic compound in step 1 is (10-30):(30-110).

[0023] Furthermore, the acyl chloride compounds mentioned in step 1 include, but are not limited to, one of acryloyl chloride and methacryloyl chloride.

[0024] Further, the molar ratio of the dynamic monomer and the acyl chloride compound in step 1 is (10-30):(30-60).

[0025] Furthermore, the stirring reaction time in step 1 is 4-24 hours.

[0026] Furthermore, the solvent used for washing in step 1 is one or more of the following: diethyl ether, saturated sodium bicarbonate aqueous solution, deionized water, or saturated sodium chloride aqueous solution.

[0027] Furthermore, the drying temperature in step 1 is 40°C, and the drying time is 8 hours.

[0028] Further, the propylene-based compound mentioned in step 2 includes, but is not limited to, one of methacrylamide, 2-hydroxyethyl acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate, ethyl acrylate, butyl acrylate, and hydroxyethyl acrylate.

[0029] Furthermore, in step 2, the long-chain alkyl group in the long-chain alkyl ester monomer contains ≥12 carbon atoms.

[0030] Furthermore, the number of carbon atoms in the long-chain alkyl group of the long-chain alkyl ester monomer is preferably 12, 14, 16, or 18.

[0031] Furthermore, the long-chain alkyl ester monomer mentioned in step 2 is preferably octadecyl methacrylate.

[0032] Further, the mass ratio of the dynamic unit, propylene compound, and long-chain alkyl ester monomer in step 2 is (0.01-0.08):(0.5-3):(2-6).

[0033] Furthermore, the initiator mentioned in step 2 includes, but is not limited to, one of 2,2-diethoxyacetophenone and benzoyl peroxide.

[0034] Furthermore, the initiation method in step 2 includes either ultraviolet light initiation or thermal initiation.

[0035] Furthermore, when using ultraviolet light initiation, a surfactant also needs to be added.

[0036] Furthermore, the surfactant includes, but is not limited to, polyoxyethylene-polyoxypropylene block copolymer (PEO-PPO-PEO), model number poloxamer F127.

[0037] Furthermore, the polymerization time described in step 2 is 1-24 hours.

[0038] Furthermore, the template used in the nanoimprinting in step 3 is anodized aluminum oxide.

[0039] Furthermore, the pore diameter of the anodic aluminum oxide is 10-300 nm, and the ratio of pore depth to pore diameter is (3-100):1.

[0040] Furthermore, the conditions for nanoimprinting in step 3 are 0.2 MPa, 70-130 °C, and 20-60 min.

[0041] Furthermore, the mass fraction of the alkaline solution in step 3 is 3-6%.

[0042] Furthermore, the solute in the alkaline solution described in step 3 is either sodium hydroxide or potassium hydroxide.

[0043] Furthermore, the etching time in step 3 is 10-12 hours.

[0044] The present invention also provides an electronic display comprising the above-described elastomer with nanoscale imprinting precision.

[0045] Furthermore, the electronic display can be applied to electronic devices with flexible components.

[0046] The beneficial effects of this invention are as follows: 1. This invention provides an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure. The imprinted layer has an imprinted structure with a minimum diameter of sub-10 nanometers and an aspect ratio of (3-100):1, where the aspect ratio is the ratio of the depth to the diameter of the imprinted structure. The water contact angle of the imprinted layer is 70-140°, thus realizing the simultaneous fabrication of a structure with nanoscale features and a high aspect ratio on the surface of the elastomer, and exhibiting good water repellency. 2. The method for preparing an elastomer with nanoscale imprinting precision according to the present invention includes the synthesis of dynamic units, the construction of dynamic heterogeneous elastomers, and nanoimprinting. Dynamic covalent bonds and crystalline phases are introduced into the dynamic heterogeneous elastomers. During the imprinting process, the elastomer network enters the nanopores of the template and is fully filled, and is reassembled into a complete network structure. The crystalline phase further restricts the resilience of the elastomer network to ensure the fidelity of the imprinted structure. That is, the elastomer is prepared by the metasomatic crystallization of the elastomer network in the nanopores. 3. The elastomer with nanoscale imprinting precision provided by the present invention can be widely used in electronic displays due to its characteristics, and its good water repellency can be adapted to electronic devices with interface performance regulation, including but not limited to electronic devices that need to have waterproof and anti-icing properties. Attached Figure Description

[0047] Figure 1 This is a SEM characterization image of an elastomer with an imprinted structure having a diameter of 100 nm, as shown in Embodiment 1 of the present invention. Figure 2 This is a comparison chart of the water contact angle tests of the elastomers in Example 1 and Comparative Example 2 of the present invention; Figure 3 The image shows the SEM characterization of the elastomer with imprinted structures having diameters of 300 nm, 200 nm, 50 nm, and sub-10 nm in Embodiment 1 of the present invention. Figure 4 These are SEM images of the elastomers with different aspect ratios in Embodiment 1 of the present invention; Figure 5 This is a SEM characterization image of the elastomer with an imprinted structure having a diameter of 100 nm in Embodiment 4 of the present invention. Figure 6 SEM characterization images of the elastomer with imprinted structures having diameters of 50 nm, 200 nm, and 400 nm in Embodiment 4 of the present invention; Figure 7 This is a SEM characterization image of the imprinted elastomer in Comparative Example 1 of the present invention. Detailed Implementation

[0048] Example 1 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of dynamic unit: 150 mL of methanol was added to a 250 mL round-bottom flask. Sodium hydroxide (4.12 g, 103 mmol) and cystine (5.57 g, 23.16 mmol) were added sequentially with stirring at room temperature. After the system temperature was lowered to 0 °C, acryloyl chloride (4.53 mL, 55.74 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 4 h to obtain the reaction solution. The reaction solution was then filtered through diatomaceous earth to obtain the filtrate. This filtrate was then added dropwise to 250 mL of diethyl ether, which had been pre-cooled at -20°C, and the mixture was stirred rapidly for 30 min. After stirring, a white precipitate appeared in the solution, which was the crude dynamic unit. After filtration, the filter cake was washed three times with cooled diethyl ether. Finally, all the crude dynamic unit was placed in a vacuum drying oven at 40°C for 8 h to obtain 2.5 g of white solid product, which was the dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of dynamic heteroelastomer: 0.02g of dynamic unit and 3g of methacrylamide were added to 2.38g of deionized water and shaken to form a prepolymer solution; then 5.18g of octadecyl methacrylate, 50μL of 2,2-diethoxyacetophenone initiator and 80μL of poloxamer F127 surfactant were added to form a two-phase mixture. The mixture was sheared at 18000rpm for 5min to form a stable and uniform oil-in-water emulsion. Finally, the emulsion was polymerized under ultraviolet light for 1h to obtain a dynamic heteroelastomer, which in this example is a dynamic heterogel emulsion; Step 3, Nanoimprinting: Using anodized aluminum with a pore diameter of 100 nm and a pore depth to pore diameter ratio of 5:1 as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press under the following conditions: 0.2 MPa, 80 °C, and 30 min. After imprinting, the elastomer is cooled to room temperature and then etched in a 5% (w / w) alkaline sodium hydroxide solution for 10 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure.

[0049] In this embodiment, the SEM characterization image of the elastomer with nanoscale imprinting precision is as follows: Figure 1 As shown, the surface of the elastomer is an imprinted layer with a nanostructure, the imprinted layer having an imprinted structure with a diameter of 100 nm and an aspect ratio of 5:1. Figure 2 As shown, B is the water contact angle test diagram of the elastomer, and the water contact angle is 123°.

[0050] In some embodiments, when anodized aluminum with different feature sizes is selected in step 3, the imprinted layer on the surface of the elastomer has different imprinted structures, such as... Figure 3 The images shown (scale bar: 100nm) are SEM characterization images of elastomers with imprinted structures having diameters of 300nm, 200nm, 50nm, and sub-10nm, respectively.

[0051] When the diameter is 50 nm, different aspect ratios of anodic aluminum oxide are selected, such as... Figure 3 The SEM images of the elastomers with different aspect ratios are shown below: A. The aspect ratio is 3:1, the diameter is 50nm, and the depth is 150nm; B. The aspect ratio is 20:1, the diameter is 50nm, and the depth is 1μm (1000nm). C. The aspect ratio is 100:1, the diameter is 50nm, and the depth is 5μm (5000nm).

[0052] Example 2 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of dynamic unit: 150 mL of methanol was added to a 250 mL round-bottom flask. Sodium hydroxide (4.12 g, 103 mmol) and cystine (5.57 g, 23.16 mmol) were added sequentially with stirring at room temperature. After the system temperature was lowered to 0 °C, acryloyl chloride (4.53 mL, 55.74 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 4 h to obtain the reaction solution. The reaction solution was then filtered through diatomaceous earth to obtain the filtrate. This filtrate was then added dropwise to 250 mL of diethyl ether, which had been pre-cooled at -20°C, and the mixture was stirred rapidly for 30 min. After stirring, a white precipitate appeared in the solution, which was the crude dynamic unit. After filtration, the filter cake was washed three times with cooled diethyl ether. Finally, all the crude dynamic unit was placed in a vacuum drying oven at 40°C for 8 h to obtain 2.5 g of white solid product, which was the dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of the dynamic heteroelastomer: 0.08g of dynamic unit and 0.81g of 2-hydroxyethyl acrylate were added to 2.19g of deionized water and shaken to form a prepolymer solution; then 5.18g of octadecyl methacrylate, 50μL of 2,2-diethoxyacetophenone initiator and 80μL of poloxamer F127 surfactant were added to form a two-phase mixture. The mixture was sheared at 18000rpm for 5min to form a stable and uniform oil-in-water emulsion. Finally, the emulsion was polymerized under ultraviolet light for 1h to obtain the dynamic heteroelastomer, which in this example is a dynamic heterogel emulsion; Step 3, Nanoimprinting: Using anodized aluminum with a pore diameter of 100 nm as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press. The imprinting conditions are 0.2 MPa, 80 °C, and 30 min. After imprinting, the elastomer is cooled to room temperature and etched in a 5% (w / w) alkaline sodium hydroxide solution for 10 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure, and the imprinted layer on the surface of the elastomer has an imprinted structure of 100 nm.

[0053] Example 3 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of dynamic unit: 150 mL of methanol was added to a 250 mL round-bottom flask. Sodium hydroxide (4.12 g, 103 mmol) and cystine (5.57 g, 23.16 mmol) were added sequentially with stirring at room temperature. After the system temperature was lowered to 0 °C, acryloyl chloride (4.53 mL, 55.74 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 4 h to obtain the reaction solution. The reaction solution was then filtered through diatomaceous earth to obtain the filtrate. This filtrate was then added dropwise to 250 mL of diethyl ether, which had been pre-cooled at -20°C, and the mixture was stirred rapidly for 30 min. After stirring, a white precipitate appeared in the solution, which was the crude dynamic unit. After filtration, the filter cake was washed three times with cooled diethyl ether. Finally, all the crude dynamic unit was placed in a vacuum drying oven at 40°C for 8 h to obtain 2.5 g of white solid product, which was the dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of the dynamic heteroelastomer: 0.27g of dynamic unit and 2.7g of 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate were added to 3.3g of deionized water and shaken to form a prepolymer solution; then 10.37g of octadecyl methacrylate, 50μL of 2,2-diethoxyacetophenone initiator and 80μL of poloxamer F127 surfactant were added to form a two-phase mixture. The mixture was sheared at 18000 rpm for 5 min to form a stable and uniform oil-in-water emulsion. Finally, the emulsion was polymerized under ultraviolet light for 1 h to obtain the dynamic heteroelastomer, which in this example is a dynamic heterogel emulsion; Step 3, Nanoimprinting: Using anodized aluminum with a pore diameter of 100 nm as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press. The imprinting conditions are 0.2 MPa, 80 °C, and 30 min. After imprinting, the elastomer is cooled to room temperature and etched in a 5% (w / w) alkaline sodium hydroxide solution for 10 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure, and the imprinted layer on the surface of the elastomer has an imprinted structure of 100 nm.

[0054] Example 4 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of the dynamic unit: Di(2-hydroxyethyl) disulfide (2.0 g, 12.97 mmol) was dissolved in 30 mL of dichloromethane, and triethylamine (5.4 mL, 38.85 mmol) was added and stirred until clear. After the system temperature was lowered to 0 °C, methacryloyl chloride (3.14 mL, 32.44 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 24 h to obtain the reaction solution. The reaction solution was then filtered to remove solids. The resulting filtrate was subjected to a series of washing steps, namely, washing with saturated sodium bicarbonate aqueous solution, deionized water and saturated sodium chloride aqueous solution in sequence. The organic phase was adsorbed with anhydrous magnesium sulfate and then separated by filtration. Finally, the solvent was evaporated and dried under reduced pressure to obtain 2.1 g of dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of dynamic heteroelastomer: 0.02g dynamic unit, 0.5g ethyl acrylate, 1.5g octadecyl methacrylate and 0.02g benzoyl peroxide initiator are mixed and stirred at 50°C for 1h. Then, thermal polymerization is carried out at 70°C for 24h to obtain dynamic heteroelastomer, which is dynamic heteroacrylic elastomer in this embodiment. Step 3, Nanoimprinting: Using anodized aluminum with a pore diameter of 100 nm and a pore depth to pore diameter ratio of 5:1 as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press under the following conditions: 0.2 MPa, 100 °C, and 60 min. After imprinting, the elastomer is cooled to room temperature and then etched in a 5% (w / w) alkaline sodium hydroxide solution for 12 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure.

[0055] In this embodiment, the SEM characterization image of the elastomer with nanoscale imprinting precision is as follows: Figure 5 As shown, the imprinted layer on the surface of the elastomer has an imprinted 100 nm structure.

[0056] In some embodiments, when anodized aluminum with different feature sizes is selected in step 3, the imprinted layer on the surface of the elastomer has different imprinted structures, such as... Figure 6 As shown, the AFM characterization of the patterns prepared by dynamic heteropolymer acrylate elastomers with different feature sizes is shown. The diameters of the imprinted structures A and D are 50 nm, the diameters of the imprinted structures B and E are 200 nm, and the diameters of the imprinted structures C and F are 400 nm. Scale bar: except for D which is 200 nm, all are 500 nm.

[0057] Example 5 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of the dynamic unit: Di(2-hydroxyethyl) disulfide (2.0 g, 12.97 mmol) was dissolved in 30 mL of dichloromethane, and triethylamine (5.4 mL, 38.85 mmol) was added and stirred until clear. After the system temperature was lowered to 0 °C, methacryloyl chloride (3.14 mL, 32.44 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 24 h to obtain the reaction solution. The reaction solution was then filtered to remove solids. The resulting filtrate was subjected to a series of washing steps, namely, washing with saturated sodium bicarbonate aqueous solution, deionized water and saturated sodium chloride aqueous solution in sequence. The organic phase was adsorbed with anhydrous magnesium sulfate and then separated by filtration. Finally, the solvent was evaporated and dried under reduced pressure to obtain 2.1 g of dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of dynamic heteroelastomer: 0.02g dynamic unit, 0.5g butyl acrylate, 2.0g octadecyl methacrylate and 0.02g benzoyl peroxide initiator are mixed and stirred at 50°C for 1h. Then, thermal polymerization is carried out at 70°C for 24h to obtain dynamic heteroelastomer, which is dynamic heteroacrylic elastomer in this embodiment. Step 3, Nanoimprinting: Using anodic aluminum oxide with a pore diameter of 100 nm as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press. The imprinting conditions are 0.2 MPa, 100 °C, and 60 min. After imprinting, the elastomer is cooled to room temperature and etched in a 5% (w / w) alkaline sodium hydroxide solution for 12 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure, and the imprinted layer on the surface of the elastomer has an imprinted structure of 100 nm.

[0058] Example 6 The preparation method of an elastomer with nanoscale imprinting precision according to this embodiment specifically includes the following steps: Step 1, Synthesis of the dynamic unit: Di(2-hydroxyethyl) disulfide (2.0 g, 12.97 mmol) was dissolved in 30 mL of dichloromethane, and triethylamine (5.4 mL, 38.85 mmol) was added and stirred until clear. After the system temperature was lowered to 0 °C, methacryloyl chloride (3.14 mL, 32.44 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 24 h to obtain the reaction solution. The reaction solution was then filtered to remove solids. The resulting filtrate was subjected to a series of washing steps, namely, washing with saturated sodium bicarbonate aqueous solution, deionized water and saturated sodium chloride aqueous solution in sequence. The organic phase was adsorbed with anhydrous magnesium sulfate and then separated by filtration. Finally, the solvent was evaporated and dried under reduced pressure to obtain 2.1 g of dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of dynamic heteroelastomer: 0.02g dynamic unit, 0.5g hydroxyethyl acrylate, 2.0g octadecyl methacrylate and 0.02g benzoyl peroxide initiator are mixed and stirred at 50°C for 1h. Then, thermal polymerization is carried out at 70°C for 24h to obtain dynamic heteroelastomer, which is dynamic heteroacrylic elastomer in this embodiment. Step 3, Nanoimprinting: Using anodic aluminum oxide with a pore diameter of 100 nm as a template, the dynamic heterogeneous elastomer is placed on the template surface and nanoimprinted in a hot press. The imprinting conditions are 0.2 MPa, 100 °C, and 60 min. After imprinting, the elastomer is cooled to room temperature and etched in a 5% (w / w) alkaline sodium hydroxide solution for 12 h to obtain an elastomer with nanoscale imprinting precision. The surface of the elastomer is an imprinted layer with a nanostructure, and the imprinted layer on the surface of the elastomer has an imprinted structure of 100 nm.

[0059] Comparative Example 1 This comparative example provides an imprinted elastomer, which, compared to Example 1, uses ethylene glycol dimethacrylate directly as the dynamic unit for preparation, and includes the following steps: Step 1: Construction of dynamic heteroelastomer: 0.02g of ethylene glycol dimethacrylate and 3g of methacrylamide were added to 2.38g of deionized water and shaken to form a prepolymer solution; then 5.18g of octadecyl methacrylate, 50μL of 2,2-diethoxyacetophenone initiator and 80μL of poloxamer F127 surfactant were added to form a two-phase mixture. The mixture was sheared at 18000 rpm for 5min to form a stable and uniform oil-in-water emulsion. Finally, the emulsion was polymerized under ultraviolet light for 1h to obtain the dynamic heteroelastomer. Step 2, Nanoimprinting: Using anodized aluminum with a pore diameter of 100 nm and an aspect ratio of 5:1 as a template, the dynamic heterogeneous elastomer is placed on the surface of the template and nanoimprinted in a hot press. The imprinting conditions are 0.2 MPa, 80 °C, and 30 min. After imprinting, the elastomer is cooled to room temperature and etched in a 5% (w / w) alkaline sodium hydroxide solution for 10 h to obtain the imprinted elastomer.

[0060] In this comparative example, the SEM characterization image of the imprinted elastomer is as follows: Figure 7 As shown.

[0061] Comparative Example 2 This comparative example does not perform step 3 of nanoimprinting compared to Example 1. The specific steps are as follows: Step 1, Synthesis of dynamic unit: 150 mL of methanol was added to a 250 mL round-bottom flask. Sodium hydroxide (4.12 g, 103 mmol) and cystine (5.57 g, 23.16 mmol) were added sequentially with stirring at room temperature. After the system temperature was lowered to 0 °C, acryloyl chloride (4.53 mL, 55.74 mmol) was added dropwise. After the addition was completed, the reaction was stirred at room temperature for 4 h to obtain the reaction solution. The reaction solution was then filtered through diatomaceous earth to obtain the filtrate. This filtrate was then added dropwise to 250 mL of diethyl ether, which had been pre-cooled at -20°C, and the mixture was stirred rapidly for 30 min. After stirring, a white precipitate appeared in the solution, which was the crude dynamic unit. After filtration, the filter cake was washed three times with cooled diethyl ether. Finally, all the crude dynamic unit was placed in a vacuum drying oven at 40°C for 8 h to obtain 2.5 g of white solid product, which was the dynamic unit. In this embodiment, the structure of the dynamic unit is as follows: ; Step 2, Construction of the dynamic heteroelastomer: 0.02g of dynamic unit and 3g of methacrylamide were added to 2.38g of deionized water and shaken to form a prepolymer. Then, 5.18g of octadecyl methacrylate, 50μL of 2,2-diethoxyacetophenone initiator and 80μL of poloxamer F127 surfactant were added to form a two-phase mixture. The mixture was sheared at 18000rpm for 5min to form a stable and uniform oil-in-water emulsion. Finally, the emulsion was polymerized under ultraviolet light for 1h to obtain the dynamic heteroelastomer, which in this example is a dynamic heterogel emulsion.

[0062] like Figure 2 As shown in Figure A, its water contact angle is 75°. By comparison, it can be seen that the elastomer prepared in this invention, with its nanoscale imprinting precision, possesses excellent water repellency due to its surface microstructure.

[0063] It should be understood that the present invention is not limited to what has been described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of the invention is limited only by the appended claims.

Claims

1. An elastomer with nanoscale imprinting precision, characterized in that, The surface of the elastomer is an imprinted layer with a nanostructure. The imprinted layer has an imprinted structure with a minimum diameter of sub-10 nanometers and an aspect ratio of (3-100):

1. The aspect ratio is the ratio of the depth to the diameter of the imprinted structure. The water contact angle of the imprinted layer is 70-140°.

2. A method for preparing an elastomer with nanoscale imprinting precision as described in claim 1, characterized in that, This includes the synthesis of dynamic units, the construction of dynamic heteroelastomers, and nanoimprinting.

3. The method for preparing an elastomer with nanoscale imprinting precision according to claim 2, characterized in that, The preparation method specifically includes the following steps: Step 1, Synthesis of dynamic unit: The dynamic monomer is dissolved in a solvent, an alkaline compound is added, the system temperature is lowered to 0℃, and then an acyl chloride compound is added dropwise. After the addition is complete, the reaction is stirred at room temperature. The reaction mixture was then filtered, washed, and dried to obtain the dynamic unit. Step 2, Construction of dynamic heteroelastomer: Dynamic units, propylene compounds, long-chain alkyl ester monomers and initiators are polymerized to obtain dynamic heteroelastomer; Step 3, Nanoimprinting: The dynamic heteroelastomer is nanoimprinted, cooled to room temperature after imprinting, and then etched in an alkaline solution to obtain an elastomer with nanoscale imprinting precision.

4. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The dynamic monomer described in step 1 contains dynamic covalent bonds.

5. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The acyl chloride compound mentioned in step 1 is one of acryloyl chloride and methacryloyl chloride.

6. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The propylene compound mentioned in step 2 is one of methacrylamide, 2-hydroxyethyl acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate, ethyl acrylate, butyl acrylate, and hydroxyethyl acrylate.

7. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The long-chain alkyl ester monomers described in step 2 contain ≥12 carbon atoms in their long-chain alkyl groups.

8. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The initiator mentioned in step 2 is one of 2,2-diethoxyacetophenone and benzoyl peroxide.

9. The method for preparing an elastomer with nanoscale imprinting precision according to claim 3, characterized in that, The template used in the nanoimprinting step 3 is anodic aluminum oxide.

10. An electronic display, characterized in that, The electronic display includes the elastomer with nanoscale imprinting precision as described in claim 1.

Images