Tough hydrogel films and their supramolecular fabrication method
A hydrogel membrane with high strength, high elongation and excellent cycle recovery performance was prepared by UV curing and metal ion coordination crosslinking, which solves the problem of insufficient mechanical properties of traditional hydrogels and is suitable for flexible electronics and biomedical applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGHUA CHUANGXIN INTELLIGENT TECHNOLOGY (HANGZHOU) CO LTD
- Filing Date
- 2026-03-05
- Publication Date
- 2026-06-02
AI Technical Summary
Traditional hydrogels have poor mechanical properties, exhibiting low strength, easy fracture, and poor resilience, which limits their reliability and durability in practical applications.
A method combining ultraviolet light curing and metal ion coordination was adopted. An initial gel film was formed by ultraviolet light curing, and the structure of the hydrogel was enhanced by immersion in a soluble zirconium salt solution to achieve coordination crosslinking between metal ions and polymer networks.
A strong and tough hydrogel membrane with high tensile strength, high elongation and excellent cycle recovery performance was prepared, which is suitable for flexible electronics and biomedical applications.
Smart Images
Figure CN122127634A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional polymer materials technology, specifically, it relates to a strong and tough hydrogel membrane and its super-assembly preparation method. Background Technology
[0002] Hydrogels are polymeric materials with a three-dimensional network structure. Due to their high water content, good biocompatibility, and flexibility, they have wide applications in tissue engineering, flexible electronics, and drug delivery. However, traditional hydrogels often exhibit poor mechanical properties, such as low strength, brittleness, and poor resilience, which severely limits their reliability and durability in practical applications. In recent years, enhancing the mechanical properties of hydrogels through physical crosslinking, dual-network structures, or metal coordination has become a research hotspot. Among these methods, the coordination between metal ions and polymer chains can significantly improve strength and toughness without sacrificing material flexibility, but existing methods often suffer from complex processes, demanding conditions, and insufficient resilience. Therefore, developing a simple, high-performance, and resilient method for preparing strong and tough hydrogel films is of great significance. Summary of the Invention
[0003] To address the shortcomings of the existing technologies, the present invention aims to provide a strong and tough hydrogel membrane and its super-assembly preparation method. This invention achieves functional enhancement of the hydrogel structure through a combination of ultraviolet light curing and metal ion coordination, resulting in a membrane with high tensile strength, high elongation, and excellent cycle recovery performance. The process of this invention is simple, the conditions are mild, and the raw materials are readily available. The resulting hydrogel membrane exhibits excellent mechanical properties and demonstrates good deformation recovery under different pressures, making it suitable for large-scale preparation of high-performance hydrogel membranes.
[0004] The technical solution of the present invention is described in detail below.
[0005] This invention provides a method for super-assembly preparation of a strong and tough hydrogel membrane, comprising the following steps: (1) Under light-protected conditions, 1~1.5 g of polyvinyl alcohol (PVA), 1~8 g of acrylic acid (AA), 2~8 g of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and 0.4~1.0 g of bis(2-methacryloyloxyethyl) phosphate (BMEP) were dissolved in a solvent to obtain a clear solution; then a photoinitiator was added to the solution and stirred until completely dissolved to obtain a precursor solution; (2) Under light-protected conditions, nitrogen gas is continuously introduced into the precursor solution to remove oxygen, and then the precursor solution is centrifuged in a centrifuge to remove gas. (3) The degassed precursor solution was solidified under ultraviolet light to form the initial gel film HM; (4) Immerse the initial hydrogel membrane HM in a soluble zirconium salt aqueous solution and soak it at room temperature for 5 to 10 days. After taking it out, wash and equilibrate it to obtain a strong and tough hydrogel membrane THM.
[0006] In step (1) above, AA acrylate, AMPS 2-acrylamide-2-methylpropanesulfonic acid and BMEP bis(2-methacryloyloxyethyl) phosphate are passed through an alkaline alumina column to remove the polymerization inhibitors before use.
[0007] In step (1) above, the average degree of polymerization of the polyvinyl alcohol (PVA) is 1650~1850 (corresponding to a number average molecular weight of about 72,600~81,400 g / mol, i.e. 72.6~81.4 kDa), and the degree of alcoholysis is 98~99% (mol / mol).
[0008] In step (1) above, the solvent is water, and the amount of water used is 8-12g.
[0009] In step (1) above, the photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone I2959, and the amount of photoinitiator added is 0.5-1.5% of the total molar amount of acrylic acid AA and 2-acrylamide-2-methylpropanesulfonic acid AMP.
[0010] In step (2) above, the nitrogen gas is passed through the precursor solution for 0.5-1.5 hours, the centrifuge speed is 10,000-13,000 rpm, and the centrifugation time is 10-20 minutes.
[0011] In step (3) above, the ultraviolet light wavelength is 365nm and the curing time is 10-20min.
[0012] The operation steps of step (3) above are carried out inside the glove box.
[0013] In step (4) above, the soluble zirconium salt solution is a 0.2-0.5 mol / L zirconium chloride aqueous solution; after soaking and removal, excess ions on the surface are rinsed with deionized water and equilibrated in deionized water for 20-30 hours. Step (4) achieves super-assembly reinforcement of the hydrogel membrane through coordination crosslinking of metal ions and polymer network.
[0014] The present invention also provides a strong and tough hydrogel membrane prepared by the above preparation method; the obtained hydrogel membrane has excellent mechanical properties, with an elongation at break of more than 100%, a tensile strength of more than 12 MPa, and maintains a high recovery rate after multiple cycles under 100% strain, and exhibits good deformation recovery ability under different pressures.
[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The preparation process is simple, requires no complex equipment, operates under mild conditions, and is easy to scale up for production.
[0016] 2. Superassembly reinforcement is achieved through zirconium ion coordination, which significantly improves the mechanical properties and resilience of the hydrogel.
[0017] 3. The resulting hydrogel membrane has high strength, high elongation and high resilience, making it suitable for a variety of flexible devices and biomedical applications. Attached Figure Description
[0018] Figure 1 (a) SEM image of the initial gel membrane in Example 1; (b) SEM image of the tough hydrogel membrane in Example 1.
[0019] Figure 2 (a) Stress-strain curve of the initial gel membrane in Example 1; (b) Stress-strain curve of the tough hydrogel membrane in Example 1.
[0020] Figure 3 (a) XRD pattern of the initial gel membrane in Example 1; (b) XRD pattern of the tough hydrogel membrane in Example 1.
[0021] Figure 4 : Recovery performance curve of the tough hydrogel membrane in Example 1 under cyclic stretching.
[0022] Figure 5 Deformation recovery curves of the tough hydrogel membrane in Example 1 under different pressures. Detailed Implementation
[0023] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments.
[0024] Example 1: Preparation of a tough hydrogel membrane (1) 2 g of PVA was added to 18 mL of deionized water and stirred in a 90 ℃ water bath until completely dissolved, then cooled to room temperature. The following raw materials were added: 6 g of AA, 10 g of AMPS, 0.8 g of BMEP, and 0.2 g of I2959. They were added to the above solution and mixed until completely dissolved to obtain a clear precursor solution. Nitrogen gas was introduced into the precursor solution for 1 h, and then the precursor solution was centrifuged at 12000 rpm for 10 min. The above operations were carried out in the dark. (2) The precursor solution and mold were transferred into a glove box. The solution was injected into the flat mold and irradiated under 365 nm ultraviolet light for 10 min. After curing, the mold was removed to obtain a transparent initial gel film with a thickness of about 1 mm. Its SEM and XRD patterns are shown below. Figure 1 (a) Figure 3 As shown in (a) in the text; (3) Immerse the initial gel membrane in a 0.3 mol / L zirconium chloride aqueous solution and let it stand at room temperature for 7 days; (4) Remove the membrane, rinse the surface with deionized water to remove excess ions, and equilibrate in deionized water for 24 hours to obtain a strong and tough hydrogel membrane. Its SEM image and XRD pattern are shown below. Figure 1 (b) Figure 3 As shown in (b) of the diagram.
[0025] Figure 2 (a) in the figure is the stress-strain curve of the initial gel film. Figure 2 (b) is the stress-strain curve of the strong and tough hydrogel film; it was measured by an electronic universal testing machine, the test mode was tensile mode, and the tensile rate was 40 mm / min (model: Instron 5966). Figure 4 The graph shows the recovery performance of the tough hydrogel membrane under cyclic stretching. Figure 5 The deformation recovery curves of the tough hydrogel membrane under different pressures were obtained using a rotational rheometer in creep-recovery mode. The deformation recovery capability of the tough hydrogel was measured by applying different pressures (brand: ThermoFisher, model: HaakeMARS III). The results show that the tough hydrogel membrane obtained in this invention has an elongation at break exceeding 100%, a tensile strength higher than 12 MPa, and maintains a high recovery rate even after multiple cycles at 100% strain, demonstrating excellent durability and deformation recovery ability.
[0026] Example 2: Preparation of a tough hydrogel membrane (1) 2 g of PVA was added to 18 mL of deionized water and stirred in a 90 ℃ water bath until completely dissolved, then cooled to room temperature. 10 g of AA, 10 g of AMPS, 1 g of BMEP, and 0.2 g of I2959 were added to the above solution and mixed until completely dissolved to obtain a clear precursor solution. Nitrogen gas was bubbled into the precursor solution for 1 h, and then the precursor solution was centrifuged at 12000 rpm for 10 min. All of the above operations were performed in the dark. (2) Transfer the precursor solution and mold and other devices into the glove box, inject the solution into the flat mold, irradiate it under 365 nm ultraviolet light for 15 min, and demold it after curing to obtain a transparent initial gel film with a thickness of about 1 mm. (3) Immerse the initial gel membrane in a 0.4 mol / L zirconium chloride aqueous solution and let it stand at room temperature for 6 days; (4) Remove the membrane, rinse the surface with deionized water to remove excess ions, and equilibrate in deionized water for 30 hours to obtain a strong and tough hydrogel membrane.
Claims
1. A method for superassembly preparation of a strong and tough hydrogel membrane, characterized in that, Includes the following steps: (1) Under light-protected conditions, 1~1.5 g of polyvinyl alcohol (PVA), 1~8 g of acrylic acid (AA), 2~8 g of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and 0.4~1.0 g of bis(2-methacryloyloxyethyl) phosphate (BMEP) were dissolved in a solvent to obtain a clear solution; then a photoinitiator was added to the solution and stirred until completely dissolved to obtain a precursor solution; (2) Under light-protected conditions, nitrogen gas is continuously introduced into the precursor solution to remove oxygen, and then the precursor solution is centrifuged in a centrifuge to remove gas. (3) The degassed precursor solution was solidified under ultraviolet light to form the initial gel film HM; (4) Immerse the initial hydrogel membrane HM in a soluble zirconium salt aqueous solution and soak it at room temperature for 5 to 10 days. After taking it out, wash and equilibrate it to obtain a strong and tough hydrogel membrane THM.
2. The preparation method according to claim 1, characterized in that, In step (1), AA acrylate, AMPS 2-acrylamide-2-methylpropanesulfonic acid and BMEP bis(2-methacryloyloxyethyl) phosphate are passed through an alkaline alumina column to remove the polymerization inhibitors before use.
3. The preparation method according to claim 1, characterized in that, In step (1), the average degree of polymerization of the polyvinyl alcohol (PVA) is 1650~1850, and the degree of alcoholysis is 98~99% (mol / mol).
4. The preparation method according to claim 1, characterized in that, In step (1), the solvent is water, and the amount of water used is 8-12g.
5. The preparation method according to claim 1, characterized in that, In step (1), the photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylphenylacetone I2959, and the amount of photoinitiator added is 0.5-1.5% of the total molar amount of acrylic acid AA and 2-acrylamide-2-methylpropanesulfonic acid AMPS.
6. The preparation method according to claim 1, characterized in that, In step (2), nitrogen gas is passed through the precursor solution for 0.5-1.5 hours, the centrifuge speed is 10,000-13,000 rpm, and the centrifugation time is 10-20 minutes.
7. The preparation method according to claim 1, characterized in that, In step (3), the ultraviolet light wavelength is 365nm and the curing time is 10-20min.
8. The preparation method according to claim 1, characterized in that, Step (3) is performed inside the glove box.
9. The preparation method according to claim 1, characterized in that, In step (4), the soluble zirconium salt solution is a 0.2-0.5 mol / L zirconium chloride aqueous solution; after soaking and removing, rinse the surface with deionized water to remove excess ions, and equilibrate in deionized water for 20-30 hours.
10. A strong and tough hydrogel membrane prepared by the preparation method according to any one of claims 1-9.