Calcium phosphate ion cluster, composite film, hydrogel film and preparation method and application thereof
By introducing calcium phosphate ion clusters into the hydrogel to form an organic-inorganic interpenetrating network structure with polyvinyl alcohol, the problem of insufficient strength and toughness of the hydrogel was solved, and high-strength and high-toughness hydrogel films were prepared.
Patent Information
- Application Number
- CN202511744923.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-25
- Publication Date
- 2026-02-10
AI Technical Summary
Existing hydrogels lack mechanical strength and toughness, and the poor dispersion of inorganic nanomaterials in nanocomposite hydrogels leads to discontinuous structures, making it difficult to achieve high strength and high toughness.
By preparing an organic-inorganic interpenetrating bicontinuous network structure formed by calcium phosphate ion clusters and polyvinyl alcohol, a high-strength and high-toughness hydrogel film is formed by utilizing the hydrogen bonding and physical cross-linking between calcium phosphate ion clusters and polyvinyl alcohol.
The hydrogel film can withstand a pull of approximately 7750 times its own weight without breaking, exhibiting excellent fracture strength and fracture toughness. The toughness can be adjusted by regulating the amount of polyvinyl alcohol.
Smart Images
Figure CN121493899A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of materials technology, and in particular to a calcium phosphate ion cluster, a composite film, a hydrogel film, and their preparation methods and applications. Background Technology
[0002] Hydrogels are soft materials with high water content and a 3D cross-linked structure composed of polymer networks, which show broad application prospects in fields such as biomedical engineering, soft robotics, and environmental research.
[0003] However, insufficient mechanical strength and lack of toughness remain the main bottlenecks restricting their practical application. Monopolymer hydrogels, composed of a single polymer network, suffer from low strength and a fracture energy <10 J / m² due to their inhomogeneous structure and lack of energy dissipation mechanisms. −2 .
[0004] Therefore, researchers developed dual-network hydrogels, improving their mechanical properties by introducing another polymer network to increase energy dissipation mechanisms. Interpenetrating dual-network hydrogels, composed of a rigid polymer network and a ductile polymer network, exhibit high toughness, overcoming the low mechanical properties of traditional single-network hydrogels. However, the interaction between organic molecules has limited impact on improving the hydrogel's strength.
[0005] To further improve the mechanical strength of hydrogels, researchers have incorporated nanoscale materials, including carbon-based nanomaterials and ceramic nanoparticles, into polymer networks to prepare nanocomposite hydrogels. However, some inorganic nanomaterials exhibit poor dispersion within polymer networks, leading to interfacial defects such as phase separation, which hinders the synergistic improvement of strength and toughness. Therefore, addressing the issue of discontinuous internal structures in nanocomposite hydrogels and constructing hydrogels with both high strength and high toughness remains a significant challenge.
[0006] In view of the problems existing in the current technology, it is very necessary to develop a new type of hydrogel film and its preparation method.
[0007] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the Invention
[0008] This application provides a calcium phosphate ion cluster, a composite film, a hydrogel film, a method for preparing the same, and its applications, in order to solve or alleviate one or more of the technical problems mentioned above.
[0009] In a first aspect, this application provides a method for preparing calcium phosphate ion clusters, characterized in that the preparation method includes: Add adenosine-5'-triphosphate disodium hydrate to calcium chloride solution to adjust the pH to 9-11, then add disodium hydrogen phosphate dodecahydrate solution to maintain the pH at 9-11. Keep the solution under stirring for 1-3 h to obtain calcium phosphate ion clusters.
[0010] Preferably, the concentration of the calcium chloride solution is 0.078-0.118 mol / L; Preferably, based on 1 mol of calcium chloride added to the calcium chloride solution, the amount of adenosine-5'-triphosphate disodium salt hydrate added is 0.060-0.068 mol; Preferably, the pH adjuster used to adjust the pH to 9-11 includes: 1M sodium hydroxide aqueous solution, 1M potassium hydroxide aqueous solution and 1M ammonia aqueous solution; Preferably, the concentration of the disodium hydrogen phosphate dodecahydrate solution is 0.084-0.126 mol / L; Preferably, the stirring rate is 500-800 rpm.
[0011] Preferably, the preparation method further includes post-processing the mixture obtained after stirring; Preferably, the post-processing is performed 1-5 times; Preferably, the post-processing includes solid-liquid separation and washing; Preferably, the solid-liquid separation method is centrifugation, and the centrifugation rate is 5000-7000 rpm for 1-10 min; Preferably, the cleaning solvent is deionized water.
[0012] Secondly, this application prepares calcium phosphate ion clusters according to the preparation method described in the first aspect.
[0013] Thirdly, this application provides a method for preparing a composite film, the method comprising: adding a polyvinyl alcohol solution to the calcium phosphate ion clusters prepared in the first aspect, stirring vigorously, and drying to obtain a composite film.
[0014] Preferably, based on the addition amount of calcium phosphate ion clusters of 0.3 g, the addition amount of the polyvinyl alcohol solution is 17-57 g; Preferably, the vigorous stirring rate is 1000-1500 rpm, and the time is 4-8 h; Preferably, the drying temperature is 10-40°C.
[0015] Fourthly, this application provides a composite film prepared according to the preparation method described in the third aspect.
[0016] Fifthly, this application provides a method for preparing a hydrogel film, the method comprising: placing the composite film prepared according to claim 5 or 6 in water for swelling for 0.5-2 h to obtain a hydrogel film.
[0017] Sixthly, this application provides a hydrogel film prepared according to the preparation method described in the fifth aspect.
[0018] The seventh aspect is the application of the composite film according to the fourth aspect, or the hydrogel film according to the sixth aspect, in the fields of biomedicine, soft robotics, or the environment.
[0019] The embodiments of this application employing the above-described technical solution may have the following advantages: In the preparation of hydrogel films, by forming an organic-inorganic interpenetrating bicontinuous network structure with inorganic calcium phosphate ion clusters and organic polyvinyl alcohol, it is possible to lift an object with a weight of about 7750 times its own weight without breaking, exhibiting excellent fracture strength and fracture toughness. In addition, hydrogels with different strengths and toughness can be obtained by adjusting the amount of polyvinyl alcohol added (17-57 g) during this process. Attached Figure Description
[0020] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.
[0021] Figure 1 This is a flowchart of the composite film and hydrogel film prepared in Example 1; Figure 2 This is an image of the hydrogel film provided in Embodiment 1 of this application; Figure 3 This is a transmission electron microscope image of the hydrogel film provided in Example 1 of this application; Figure 4 These are the tensile strength test diagrams of the hydrogel film and the comparative film provided in Example 1 of this application; Figure 5 These are fracture toughness test diagrams of the hydrogel film and the comparative film provided in Example 1 of this application. Detailed Implementation
[0022] The embodiments of this application are described in detail below, examples of which are illustrated in the accompanying drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Throughout, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.
[0023] It should be understood that when an element or layer is referred to as "on," "adjacent to," "connected to," or "coupled to" other elements or layers, it may be directly on, adjacent to, connected to, or coupled to other elements or layers, or there may be intervening elements or layers. Conversely, when an element is referred to as "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" other elements or layers, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc., may be used to describe various elements, components, areas, layers, and / or portions, these elements, components, areas, layers, and / or portions should not be limited by these terms. These terms are only used to distinguish one element, component, area, layer, or portion from another element, component, area, layer, or portion. Therefore, without departing from the teachings of this application, the first element, component, area, layer, or portion discussed below may be referred to as a second element, component, area, layer, or portion. And the discussion of a second element, component, area, layer, or portion does not imply that the first element, component, area, layer, or portion necessarily exists in this application.
[0024] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise expressly limited. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.
[0025] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.
[0026] In this application, when numerical intervals (i.e., numerical ranges) are involved, unless otherwise specified, the distribution of selectable numerical values within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.
[0027] This application provides a method for preparing a gel, the gel itself, composite cement, and application technology. Details are provided below.
[0028] Exemplary embodiments according to this application will now be described in more detail with reference to the accompanying drawings. It should be understood that these exemplary embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.
[0029] This application provides a method for preparing calcium phosphate ion clusters, the method comprising: Add adenosine-5'-triphosphate disodium hydrate to a calcium chloride solution to adjust the pH to 9-11 (e.g., 9, 9.5, 10, 10.5, or 11), then add disodium hydrogen phosphate dodecahydrate solution to maintain the pH at 9-11 (e.g., 9, 9.5, 10, 10.5, or 11), and keep the solution stirred for 1-3 h (e.g., 1 h, 1.5 h, 2 h, 2.5 h, or 3 h) to obtain calcium phosphate ion clusters.
[0030] In this application, by controlling the reaction pH to an alkaline environment of 9–11 and using adenosine-5'-triphosphate disodium salt (ATP) as a stabilizer, excessive crystallization and aggregation of calcium phosphate are effectively inhibited, forming ultra-small (approximately 1.7 nm) calcium phosphate ion clusters. This structure possesses high specific surface area and good dispersibility, laying the foundation for the subsequent construction of a uniform organic-inorganic composite network.
[0031] The calcium phosphate ion clusters obtained in this application have an amorphous structure and an ultra-high specific surface area, which can effectively form hydrogen bonds with polyvinyl alcohol (PVA) molecular chains to form strong interfacial bonds, providing enhanced mechanical properties and structural continuity for composite films.
[0032] In some embodiments, the concentration of the calcium chloride solution is 0.078-0.118 mol / L (e.g., 0.078 mol / L, 0.08 mol / L, 0.098 mol / L, 0.1 mol / L, 0.11 mol / L, 0.115 mol / L, 0.118 mol / L, etc.). In some embodiments, based on the amount of calcium chloride added to the calcium chloride solution being 1 mol, the amount of adenosine-5'-triphosphate disodium hydrate added is 0.060-0.068 mol (e.g., 0.060 mol / L, 0.062 mol / L, 0.065 mol / L, 0.068 mol / L, etc.). In some embodiments, the pH adjuster used to adjust the pH to 9-11 (e.g., 9, 9.5, 10, 10.5, or 11, etc.) includes: 1M sodium hydroxide aqueous solution, 1M potassium hydroxide aqueous solution, and 1M ammonia aqueous solution; In some embodiments, the concentration of the disodium hydrogen phosphate dodecahydrate solution is 0.084-0.126 mol / L (e.g., 0.084 mol / L, 0.09 mol / L, 0.1 mol / L, 0.11 mol / L, 0.12 mol / L, 0.126 mol / L, etc.). In some embodiments, the stirring rate is 500-800 rpm (e.g., 500 rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, 800 rpm, etc.).
[0033] In some embodiments, the preparation method further includes post-processing the mixture obtained after stirring; In some embodiments, the number of post-processing steps is 1-5 (e.g., 1, 2, 3, 4, 5). In some embodiments, the post-processing includes solid-liquid separation and washing; In some embodiments, the solid-liquid separation is performed by centrifugation at a speed of 5000-7000 rpm (e.g., 5000 rpm, 5500 rpm, 6000 rpm, 6500 rpm, 7000 rpm, etc.) for a time of 1-10 min (e.g., 1 min, 3 min, 5 min, 7 min, 10 min, etc.). In some embodiments, the cleaning solvent is deionized water.
[0034] In some embodiments, this application provides a method for preparing a composite film, the method comprising: adding a polyvinyl alcohol solution to the calcium phosphate ion clusters prepared above, stirring vigorously, and drying to obtain a composite film.
[0035] In this application, calcium phosphate ion clusters are mixed with a polyvinyl alcohol (PVA) solution and then vigorously stirred to promote the uniform dispersion of the inorganic phase within the organic network, forming an organic-inorganic bicontinuous structure. This structure is cured during the drying process through hydrogen bonding and physical cross-linking, endowing the film with high initial strength and toughness.
[0036] In some embodiments, based on the addition amount of calcium phosphate ion clusters being 0.3 g, the addition amount of the polyvinyl alcohol solution is 17-57 g (e.g., 17 g, 20 g, 25 g, 30 g, 35 g, 40 g, 45 g, 50 g, 55 g, 57 g, etc.). In some embodiments, the rate of vigorous stirring is 1000-1500 rpm (e.g., 1000 rpm, 1100 rpm, 1200 rpm, 1300 rpm, 1400 rpm, 1500 rpm, etc.), and the time is 4-8 h (e.g., 4 h, 5 h, 6 h, 7 h, 8 h, etc.). In some embodiments, the drying temperature is 10-40°C (e.g., 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.).
[0037] In some embodiments, this application provides a method for preparing a hydrogel film, the method comprising: placing the composite film prepared above in water for swelling for 0.5-2 h (e.g., 0.5 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, etc.) to obtain a hydrogel film.
[0038] In this application, the composite film is immersed in water to swell, and water molecules enter the network structure, which relaxes the PVA segments and forms a hydrated layer. At the same time, calcium phosphate ion clusters serve as cross-linking points to maintain network stability, ultimately forming a high-water-content, high-strength, and high-toughness bicontinuous network hydrogel.
[0039]
Example 1
[0040] This embodiment also provides a method for preparing a composite thin film, such as... Figure 1 As shown, it includes: Add 30 g of a 15 wt% polyvinyl alcohol aqueous solution to the calcium phosphate ion clusters obtained above, shake until homogeneous, transfer to a 100 mL beaker, and then vigorously stir the emulsion for 6 hours at a stirring rate of 1200 rpm to carry out the organic-inorganic crosslinking process; finally, after ultrasonic degassing the homogeneous emulsion, transfer it to a 13 cm × 13 cm petri dish, dry at room temperature of 25 °C, and finally peel it off from the petri dish to obtain a dry composite film.
[0041] This embodiment also provides a method for preparing a hydrogel film, such as... Figure 1 As shown, it includes: The composite film was immersed in water for 1 hour to reach swelling equilibrium, eventually forming a hydrogel film.
[0042] Figure 2 The hydrogel film prepared in Example 1 shows that the hydrogel film has a uniform appearance, is transparent, and has a smooth surface without obvious defects.
[0043] Figure 3 The image shown is a transmission electron microscope (TEM) image of the hydrogel film prepared in Example 1, with a scale bar of 20 nm. It can be seen that the hydrogel film exhibits an organic-inorganic interpenetrating double continuous network structure.
[0044] Figure 4The images show the fracture strength test results of the hydrogel film prepared in Example 1 and the comparative film. It can be seen that the hydrogel film formed by polyvinyl alcohol and calcium phosphate ion clusters has better fracture strength (32.89 MPa) compared to polyvinyl alcohol alone, or the combination of polyvinyl alcohol and hydroxyapatite.
[0045] Figure 5 The fracture toughness diagrams for the hydrogel film prepared in Example 1 and the comparative film show that the hydrogel film formed by polyvinyl alcohol and calcium phosphate ion clusters has better fracture toughness (108.50 MJ / m²) compared to polyvinyl alcohol alone, or the combination of polyvinyl alcohol and hydroxyapatite. -3 ).
[0046]
Example 2
[0047] The hydrogel film prepared in this application was tested using the same methods as in Example 1. The results showed that the hydrogel film also had a uniform appearance, was transparent, and had a smooth, defect-free surface. Transmission electron microscopy revealed that the hydrogel film exhibited an organic-inorganic interpenetrating double continuous network structure. The hydrogel film also possessed high strength (23.72 MPa) and high toughness (87.75 MJ / m²). -3 ).
[0048]
Example 3
[0049] In the preparation of the hydrogel film, the swelling time is 2 h.
[0050] The hydrogel film prepared in this application was tested using the same methods as in Example 1. The results showed that the hydrogel film also had a uniform appearance, was transparent, and had a smooth, defect-free surface. Transmission electron microscopy revealed that the hydrogel film exhibited an organic-inorganic interpenetrating double continuous network structure. The hydrogel film also possessed high strength (24.81 MPa) and high toughness (95.85 MJ / m²). -3 ).
[0051] It should be noted that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The directional terms "inner" and "outer" refer to the inside or outside relative to the outline of the component itself. For example, if a device in the drawings is inverted, a device described as "above" or "on top of" other devices or structures will subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.
[0052] It should also be noted that the terms "one embodiment," "another embodiment," and "embodiment" used in this application refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment described in the general description of this application. The appearance of the same expression in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure, or characteristic is described in connection with any embodiment, the intention is to suggest that implementing such a feature, structure, or characteristic in conjunction with other embodiments also falls within the scope of this application.
[0053] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.
[0054] It should also be noted that the above are merely preferred embodiments of this application and do not limit the scope of patent protection of this application. Any equivalent structural or procedural changes made using the content of this application’s specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of this application.
Claims
1. A method for preparing calcium phosphate ion clusters, characterized in that, The preparation method includes: Add adenosine-5'-triphosphate disodium hydrate to calcium chloride solution to adjust the pH to 9-11, then add disodium hydrogen phosphate dodecahydrate solution to maintain the pH at 9-11. Keep the solution under stirring for 1-3 h to obtain calcium phosphate ion clusters.
2. The preparation method according to claim 1, characterized in that, The concentration of the calcium chloride solution is 0.078-0.118 mol / L; Preferably, based on 1 mol of calcium chloride added to the calcium chloride solution, the amount of adenosine-5'-triphosphate disodium salt hydrate added is 0.060-0.068 mol; Preferably, the pH adjuster used to adjust the pH to 9-11 includes: 1M sodium hydroxide aqueous solution, 1M potassium hydroxide aqueous solution and 1M ammonia aqueous solution; Preferably, the concentration of the disodium hydrogen phosphate dodecahydrate solution is 0.084-0.126 mol / L; Preferably, the stirring rate is 500-800 rpm.
3. The preparation method according to claim 1, characterized in that, The preparation method further includes post-processing the mixture obtained after stirring; Preferably, the post-processing is performed 1-5 times; Preferably, the post-processing includes solid-liquid separation and washing; Preferably, the solid-liquid separation method is centrifugation, and the centrifugation rate is 5000-7000 rpm for 1-10 min; Preferably, the cleaning solvent is deionized water.
4. Calcium phosphate ion clusters are prepared according to any one of claims 1-3.
5. A method for preparing a composite thin film, characterized in that, The preparation method includes: A polyvinyl alcohol solution is added to the calcium phosphate ion cluster prepared according to any one of claims 1-3, the mixture is stirred vigorously, and then dried to obtain a composite film.
6. The preparation method according to claim 5, characterized in that, Based on an addition amount of 0.3 g of calcium phosphate ion clusters, the addition amount of the polyvinyl alcohol solution is 17-57 g; Preferably, the vigorous stirring rate is 1000-1500 rpm, and the time is 4-8 h; Preferably, the drying temperature is 10-40°C.
7. A composite film is prepared by the preparation method according to claim 5 or 6.
8. A method for preparing a hydrogel film, characterized in that, The preparation method includes: placing the composite film prepared according to claim 5 or 6 in water to swell for 0.5-2 h to obtain a hydrogel film.
9. A hydrogel film is prepared by the preparation method according to claim 8.
10. The composite film according to claim 7, or the hydrogel film according to claim 9, in the fields of biomedicine, soft robotics, or environment.