A hydrogel material and a preparation method and application thereof
By combining three-dimensional cross-linked network hydrogel materials formed by polyimide and polyvinylpyrrolidone or polyisopropylacrylamide with 3D printing technology, the problems of insufficient mechanical properties and anti-swelling properties of hydrogel materials have been solved, and the multi-layer structure of artificial cartilage has been prepared with good biocompatibility and modulus gradient characteristics.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-03-24
- Publication Date
- 2026-03-31
AI Technical Summary
Existing hydrogel materials cannot simultaneously possess excellent mechanical properties and anti-swelling properties, which limits their application in the field of artificial cartilage.
Artificial cartilage was prepared by using hydrogel materials with polyimide and polyvinylpyrrolidone or polyisopropylacrylamide as components, forming a three-dimensional cross-linked network structure through molecular chain entanglement, and then combining it with 3D printing technology.
This study achieved a hydrogel material that possesses both excellent mechanical properties and water absorption and swelling properties, good biocompatibility, and can meet the multi-layer structure requirements of artificial cartilage, while closely resembling the gradient modulus characteristics of real cartilage.
Smart Images

Figure CN114874461B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of polymer materials technology, and in particular relates to a hydrogel material, its preparation method and application. Background Technology
[0002] Articular cartilage is an important weight-bearing tissue in the human body, bearing the load of joints. Cartilage tissue is composed of collagen, chondrocytes, and 60-80% water. Due to the lack of nerves and blood vessels in articular cartilage, its regenerative capacity after injury is low. Therefore, artificial articular cartilage is increasingly used in the field of cartilage tissue repair. Materials and methods for preparing artificial articular cartilage have attracted widespread attention. Hydrogel materials have become an excellent choice for preparing artificial cartilage due to their excellent biocompatibility; however, existing hydrogel materials often lack both excellent mechanical properties and anti-swelling properties, limiting their application in the field of artificial cartilage. Summary of the Invention
[0003] This application provides a hydrogel material, its preparation method, and its application, aiming to solve the problem that existing hydrogel materials cannot simultaneously possess excellent mechanical properties and water absorption and swelling properties.
[0004] On one hand, embodiments of this application provide a hydrogel material comprising component A and component B, wherein component A is polyimide; and component B is polyvinylpyrrolidone or polyisopropylacrylamide, wherein the molecular chains of component A and component B are entangled to form a three-dimensional cross-linked network structure, wherein 0 < C A <1,C A The mass fraction of component A.
[0005] In another aspect, embodiments of this application provide a method for preparing the above-mentioned hydrogel material, comprising the following steps:
[0006] (1) Dissolve component A and component B in an organic solvent to obtain a mixed solution, wherein the ratio of component A to component B is controlled to obtain different C values. A A mixed solution of values;
[0007] (2) The mixed solution is heated to remove the organic solvent, so that the molecular chains of component A and component B are entangled to form a three-dimensional cross-linked network structure, thereby obtaining a hydrogel material.
[0008] Preferably, when the C A Satisfying 0.025 < C A When <0.375, the Young's modulus of the hydrogel material is 0.005 to 22.57 MPa.
[0009] Preferably, when the CA Satisfying 0.025 < C A When <0.375, the equilibrium water absorption rate of the hydrogel material is 127.8% to 725.0%.
[0010] This application also provides an application of the above-mentioned hydrogel material in artificial cartilage.
[0011] Preferably, the above application includes the following steps:
[0012] (1) Dissolve component A and component B in an organic solvent to obtain solution A and solution B respectively;
[0013] (2) The A solution and the B solution are blended in a 3D printing system, and the blended solution is used as ink for 3D printing. The organic solvent is removed by heating to obtain an artificial cartilage structure.
[0014] In the 3D printing process, the blending ratio of solution A and solution B is controlled to obtain different C values. A A blended solution of the value.
[0015] Preferably, during the 3D printing process, controlling the blending ratio of solution A and solution B includes controlling the flow rate of solution A and solution B into the 3D printing system so that the blending ratio of the blended liquid is controlled.
[0016] Preferably, during the 3D printing process, controlling the flow rate of solution A and solution B into the 3D printing system includes: introducing solution A into the 3D printing system through a dispensing tube A, introducing solution B into the 3D printing system through a dispensing tube B, and adjusting the pressure applied to the dispensing tubes A and B to control the flow rate of solution A and solution B.
[0017] Preferably, the application includes the following steps:
[0018] (1) Dissolve component A and component B in an organic solvent to obtain a mixed solution, wherein the ratio of component A to component B is controlled to obtain different C values. A A mixed solution of values;
[0019] (2) The mixed solution is used as ink for 3D printing, and the organic solvent is removed by heating to obtain an artificial cartilage structure.
[0020] Preferably, when the C A Satisfying 0.025 < C A When <0.333, the compressive modulus of the artificial cartilage structure is 0.08 to 4.36 MPa.
[0021] The hydrogel material provided in this application has both excellent mechanical properties and water absorption and swelling properties. When the mass fraction of component A (polyimide) is changed, the mechanical properties and water absorption and swelling properties of the material can be adjusted within a wide range, which can meet the requirements of hydrogel materials for mechanical properties and water absorption and swelling properties.
[0022] The hydrogel material provided in this application embodiment does not contain small molecule additives, has almost no cytotoxicity, and has good biocompatibility.
[0023] The hydrogel material provided in this application embodiment can be applied to artificial cartilage, and the resulting artificial cartilage structure can be a multilayer structure with multiple moduli, which can meet the gradient modulus characteristics of real cartilage tissue. Attached Figure Description
[0024] The features, advantages, and technical effects of exemplary embodiments of this application will now be described with reference to the accompanying drawings.
[0025] Figure 1 This is a flowchart illustrating the preparation process of the hydrogel material provided in this application;
[0026] Figure 2 These are schematic diagrams and physical images of the dual-dispensing tube in-situ blending 3D printing system provided in this application;
[0027] Figure 3 This is a graph showing the relationship between PVP concentration, PI concentration and printability during the printing process of the hydrogel material provided in this application;
[0028] Figure 4 This is a graph showing the relationship between viscosity and shear rate of PVP / PI solutions with different PVP and PI concentrations during the preparation of the hydrogel material provided in this application.
[0029] Figure 5 These are schematic diagrams and physical images of ink-direct writing 3D printing using PVP / PI solution as ink, as provided in this application.
[0030] Figure 6 This is a 3D structural image of the PVP / PI hydrogel material printed in this application.
[0031] Figure 7 This is a stress-strain curve diagram of PVP / PI hydrogel materials with different PI mass fractions provided in this application;
[0032] Figure 8 These are environmental scanning electron microscope images of PVP / PI hydrogel materials with different PI mass fractions provided in this application (where (a) has a PI mass fraction of 0.025; (b) has a PI mass fraction of 0.125; (c) has a PI mass fraction of 0.25; and (d) has a PI mass fraction of 0.375).
[0033] Figure 9 This is a diagram showing the equilibrium water absorption rate of PVP / PI hydrogel materials with different PI mass fractions provided in this application.
[0034] Figure 10 This is a compressive stress-strain curve of the artificial cartilage structure provided in this application;
[0035] Figure 11 This is a diagram of a 3D-printed multilayer artificial cartilage structure based on PVP / PI hydrogel material provided in this application;
[0036] Figure 12 The graph shows the cell proliferation and toxicity test results of PVP / PI hydrogel materials with different PI qualities. Detailed Implementation
[0037] The embodiments of this application will be described in further detail below with reference to the accompanying drawings and examples. The detailed description of the following embodiments and the accompanying drawings are used to illustrate the principles of this application by way of example, but should not be used to limit the scope of this application, that is, this application is not limited to the described embodiments.
[0038] Hydrogel materials have been extensively studied for the fabrication of artificial cartilage, but they also face many challenges. For example, hydrogel materials need to meet certain mechanical properties to provide effective physical support for hydrogel-based artificial cartilage. They also need good anti-swelling ability to maintain excellent mechanical properties stably in humid environments such as within organisms. Furthermore, hydrogel materials need to be easily and quickly processed to fabricate porous structures and various complex shapes, meeting customized fabrication needs. 3D printing, as a rapid and controllable customized processing method, has greatly facilitated the fabrication of hydrogel-based artificial cartilage. Therefore, hydrogel materials with excellent mechanical properties, anti-swelling properties, biocompatibility, and 3D printability are key technologies for the fabrication of hydrogel-based artificial cartilage.
[0039] Generally speaking, chemically cross-linked hydrogels require the addition of various small molecule additives (such as photoinitiators) during their preparation, and these additives can severely affect the biocompatibility of the hydrogel. Physically cross-linked hydrogels, on the other hand, do not require additional additives during their formation; therefore, they are generally more biocompatible than chemically cross-linked hydrogels.
[0040] On one hand, embodiments of this application provide a hydrogel material comprising component A and component B, wherein component A is polyimide; and component B is polyvinylpyrrolidone or polyisopropylacrylamide, wherein the molecular chains of component A and component B are entangled to form a three-dimensional cross-linked network structure, wherein 0 < C A <1,C AThe mass fraction of component A.
[0041] In the embodiments of this application, component A is a polyimide, such as Matrimid 5218 from BASF and other polyimide materials that can form a homogeneous solution of polyvinylpyrrolidone. Component A can be replaced by other soluble polyimides or other polymers that can dissolve in organic solvents but cannot dissolve in water.
[0042] Component B can also be replaced by hydrophilic molecular chains such as polyisopropylacrylamide that are miscible with polyimide.
[0043] The hydrogel material provided in this application has both good mechanical properties and water absorption and swelling properties. When the mass fraction of component A (polyimide) is changed, the mechanical properties and water absorption and swelling properties of the material can be adjusted within a wide range, which can meet the requirements of artificial cartilage for the mechanical properties and water absorption and swelling properties of the material.
[0044] The hydrogel material provided in this application embodiment does not contain small molecule additives, has almost no cytotoxicity, and has good biocompatibility.
[0045] On the other hand, embodiments of this application provide a method for preparing the above-mentioned hydrogel material, comprising the following steps:
[0046] (1) Dissolve component A and component B in an organic solvent to obtain a mixed solution, wherein the ratio of component A to component B is controlled to obtain different C values. A A mixed solution of values;
[0047] (2) The mixed solution is heated to remove the organic solvent, so that the molecular chains of component A and component B are entangled to form a three-dimensional cross-linked network structure, thereby obtaining a hydrogel material.
[0048] In the embodiments of this application, the hydrogel can be prepared by the following method:
[0049] A certain amount of polyvinylpyrrolidone powder (PVP) and a certain amount of soluble polyimide powder (PI) are dissolved in N,N-dimethylformamide solvent and stirred to form a homogeneous solution (PVP / PI solution).
[0050] The solution was prepared into a thin film, and the solvent was removed by heating to evaporate the solvent, resulting in a PVP / PI hydrogel material that can absorb water and swell but does not dissolve in water. The preparation process of the PVP / PI hydrogel is as follows: Figure 1 As shown in (a), this illustrates that PVP and PI molecular chains form a three-dimensional cross-linked network. This is due to the numerous entanglements between the polymer molecular chains, such as... Figure 1As shown in (b), the entanglement types in PVP / PI hydrogels are divided into three categories: entanglement between PI molecular chains, entanglement between PVP molecular chains, and entanglement between PVP and PI molecular chains. Experiments have shown that PVP-PVP entanglement can be disrupted by water. Therefore, when the mass fraction of PI in the PVP / PI hydrogel is 0, the PVP / PI hydrogel can redissolve in water, meaning that the molecular chains of the hydrogel do not form a three-dimensional cross-linked network. When the mass fraction of PI is not 0, even a small amount of PI (mass fraction of 0.025) can form stable cross-linking points due to the entanglement of PI, allowing PVP / PI to absorb water and swell in water, but it will not redissolve.
[0051] In the embodiments of this application, when the C A Satisfying 0.025 < C A When <0.375, the Young's modulus of the hydrogel material is 0.005 to 22.57 MPa.
[0052] The hydrogel material provided in this application has a higher Young's modulus than biological cartilage, and its adjustable range is wider than that of cartilage, thus meeting the requirements of artificial cartilage materials for Young's modulus.
[0053] In the embodiments of this application, when the C A Satisfying 0.025 < C A When <0.375, the equilibrium water absorption rate of the hydrogel material is 127.8% to 725.0%.
[0054] The main reason for the change in equilibrium water absorption rate with PI mass fraction is the difference in entanglement density of PI in PVP / PI hydrogel and the resulting structural compactness.
[0055] In another aspect, embodiments of this application provide an application of the above-mentioned hydrogel material in artificial cartilage.
[0056] In embodiments of this application, the application includes the following steps:
[0057] (1) Dissolve component A and component B in an organic solvent to obtain solution A and solution B respectively;
[0058] (2) Solution A and solution B were blended in a 3D printing system, and the blended solution was used as ink for 3D printing. The solvent was removed by heating to obtain artificial cartilage material.
[0059] In the 3D printing process, the mixing ratio of solution A and solution B is controlled to obtain different C values. A A blended solution of the value.
[0060] In an embodiment of this application, controlling the blending ratio of solution A and solution B during the 3D printing process includes controlling the flow rate of solution A and solution B into the 3D printing system so that the blending ratio of the blended liquid is controlled.
[0061] In an embodiment of this application, controlling the flow rate of solution A and solution B into the 3D printing system during the 3D printing process includes: introducing solution A into the 3D printing system through a dispensing tube A, introducing solution B into the 3D printing system through a dispensing tube B, and adjusting the pressure applied to the dispensing tubes A and B to control the flow rate of solution A and solution B.
[0062] In some embodiments, build as Figure 2 The illustrated in-situ blending dual-dispensing-tube 3D printing system comprises two dispensing tubes: tube A contains PVP solution, and tube B contains PI solution. One end of each tube is connected to a pressure control pump and an air compressor to provide the pressure required for ink extrusion. The other ends are connected together via a T-junction, with the third port of the T-junction connected to a plastic blending tube. This blending tube forms a homogeneous PVP / PI solution, which is then extruded through a needle tip. By adjusting the pressure applied by tubes A and B, the flow rates of the PVP and PI solutions entering the blending tube can be controlled, thereby adjusting the mass fraction of PI in the extruded PVP / PI solution. This allows for the printing of multilayer structures with different PI mass fractions.
[0063] In embodiments of this application, the application includes the following steps:
[0064] (1) Dissolve component A and component B in an organic solvent to obtain a mixed solution, wherein the ratio of component A to component B is controlled to obtain different C values. A A mixed solution of values;
[0065] (2) The mixed solution is used as ink for 3D printing, and the solvent is removed by heating to obtain artificial cartilage material.
[0066] In the embodiments of this application, PVP / PI solution is used as ink, and an artificial cartilage structure based on PVP / PI hydrogel is prepared by ink direct writing 3D printing method.
[0067] The concentrations of PVP and PI in the PVP / PI solution are adjusted to allow the solution to be extruded from the nozzle of the ink-to-printer, ensuring the formation of a continuous and stable filament. In other words, the viscosity of the PVP / PI solution is adjusted to make it usable as ink for ink-to-printer 3D printing. The concentrations of PVP and PI in the ink are related to printability as follows: Figure 3 As shown, when the concentrations of PVP and PI are low, the ink viscosity is too low, and there is no support for extrusion from the needle tip, which cannot meet the printing requirements; when the concentrations of PVP and PI are too high, the ink viscosity is too high, and it cannot be extruded from the needle tip. Figure 4 The variation of viscosity of PVP / PI solution with shear rate, obtained by rotational rheology testing, is presented. Figure 4 It can be seen that the higher the concentration of PVP and PI, the higher the viscosity of the ink; furthermore, the ink exhibits good shear thinning properties, meeting the requirements of ink-to-ink 3D printing. A schematic diagram of the 3D printing device and a photograph of the actual equipment are shown below. Figure 5 As shown in the figure. The printed artificial cartilage structure can be designed according to requirements.
[0068] The method for preparing the hydrogel material provided in this application embodiment can prepare artificial cartilage of various complex shapes and customized forms. The artificial cartilage can be a multilayer structure with multiple moduli, which can meet the gradient modulus characteristics of real cartilage tissue.
[0069] In some embodiments, the organic solvent includes one or more of N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.
[0070] Since no small molecule additives (such as initiators, crosslinking agents, monomers, etc.) are used in the preparation of hydrogel materials, the prepared hydrogel materials have good biocompatibility.
[0071] In the embodiments of this application, when the C A Satisfying 0.025 < C A When <0.333, the compressive modulus of the artificial cartilage structure is 0.08 to 4.36 MPa.
[0072] The main reason why the compressive modulus of artificial cartilage structures changes with the mass fraction of PI is the difference in the entanglement density of PI in PVP / PI hydrogels and the resulting structural compactness.
[0073] The hydrogel materials, their preparation methods, and applications provided in this application have the following advantages:
[0074] (1) The hydrogel material provided in this application utilizes the entanglement of hydrophobic molecular chains to form a novel PVP / PI hydrogel material with excellent mechanical properties, anti-swelling properties, and biocompatibility. This hydrogel material has excellent mechanical properties and anti-swelling properties.
[0075] (2) This application proposes to use PVP / PI solution as ink to prepare artificial cartilage structures based on PVP / PI hydrogels using an ink-to-ink 3D printing method. This facilitates the processing of PVP / PI hydrogels into various complex shapes and customized fabrications.
[0076] (3) This application also proposes a 3D printing method for a multilayer PVP / PI artificial cartilage structure with multiple moduli using an in-situ blending method. Given that real biological tissues such as cartilage have modulus gradients, the multilayer structure is closer to the properties of real cartilage.
[0077] Example
[0078] The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on weight, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.
[0079] Example 1
[0080] 1) Add 12 mL of N,N-dimethylformamide solution to a 50 mL beaker, then add 3 g of PI powder and stir to dissolve. Next, add 5 g of PVP powder and mechanically stir for 12 hours to mix thoroughly. This yields a PVP / PI solution with a PVP concentration of 0.25 and a PI concentration of 0.15. The viscosity and printability of the PVP / PI solution are as follows: Figure 3 and Figure 4 As shown.
[0081] 2) Load the obtained PVP / PI solution into a dispensing tube. Connect one end of the dispensing tube to a pressure controller and a compressed air compressor, and the other end to a dispensing needle. Select a dispensing needle with an inner diameter of 0.41mm. Load the prepared dispensing tube into the 3D printing equipment. A schematic diagram and actual image of the printing equipment are shown below. Figure 5 As shown.
[0082] 3) Import the pre-written gcode of the thin film sample into the 3D printer, set the pressure of the dispensing tube to 600 kPa, and start printing.
[0083] 4) Place the printed sample in an oven and heat at 70℃ for 12 hours, then at 140℃ for 12 hours. During the heating process, the solvent evaporates, resulting in a PVP / PI hydrogel material with a PI mass fraction of 0.375.
[0084] 5) Place the printed sample in pure water for 34 hours, and test the tensile stress-strain curve, environmental scanning electron microscope image, and equilibrium water absorption rate of the sample. The results are as follows: Figure 7 , Figure 8 and Figure 9As shown.
[0085] Example 2
[0086] 1) Add 12 mL of N,N-dimethylformamide solution to a 50 mL beaker, then add 3 g of PI powder and stir to dissolve. Next, add 5 g of PVP powder and mechanically stir for 12 hours to mix thoroughly. This yields a PVP / PI solution with a PVP concentration of 0.25 and a PI concentration of 0.15. The viscosity and printability of the PVP / PI solution are as follows: Figure 3 and Figure 4 As shown.
[0087] 2) Load the obtained PVP / PI solution into a dispensing tube. Connect one end of the dispensing tube to a pressure controller and a compressed air compressor, and the other end to a dispensing needle. Select a dispensing needle with an inner diameter of 0.41mm. Load the prepared dispensing tube into the 3D printing equipment. A schematic diagram and actual image of the printing equipment are shown below. Figure 5 As shown.
[0088] 3) Import the pre-written gcode code of the truss structure into the 3D printer, set the pressure of the dispensing tube to 600kPa, and start printing.
[0089] 4) Place the printed sample in an oven and heat at 70℃ for 12 hours, then at 140℃ for 12 hours. During the heating process, the solvent evaporates, resulting in a PVP / PI hydrogel material with a PI mass fraction of 0.375.
[0090] 5) The printed structure is as follows Figure 6 As shown.
[0091] Example 3
[0092] 1) Add 12 mL of N,N-dimethylformamide solution to a 50 mL beaker, then add 2 g of PI powder and stir to dissolve. Next, add 6 g of PVP powder and mechanically stir for 12 hours to mix thoroughly. This yields a PVP / PI solution with a PVP concentration of 0.30 and a PI concentration of 0.10. The viscosity and printability of the PVP / PI solution are as follows: Figure 3 and Figure 4 As shown.
[0093] 2) Load the obtained PVP / PI solution into the dispensing tube. Connect one end of the dispensing tube to the pressure controller and the compressed air machine, and connect the other end of the dispensing tube to the dispensing needle. Select a dispensing needle with an inner diameter of 0.41mm. Load the prepared dispensing tube into the 3D printing equipment.
[0094] 3) Import the pre-written gcode of the thin film sample into the 3D printer, set the pressure of the dispensing tube to 600 kPa, and start printing.
[0095] 4) Place the printed sample in an oven and heat at 70℃ for 12 hours, then at 140℃ for 12 hours. During the heating process, the solvent evaporates, resulting in a PVP / PI artificial cartilage material with a PI mass fraction of 0.25.
[0096] 5) Place the printed sample in pure water for 34 hours, and test the tensile stress-strain curve, environmental scanning electron microscope image, and equilibrium water absorption rate of the sample. The results are as follows: Figure 7 , Figure 8 and Figure 9 As shown.
[0097] Example 4
[0098] 1) Add 12 mL of N,N-dimethylformamide solution to a 50 mL beaker, then add 8 g of PI powder, stir to dissolve, and obtain a PI solution with a PI concentration of 0.4.
[0099] 2) Add 12 mL of N,N-dimethylformamide solution to a 50 mL beaker, then add 8 g of PVP powder, stir to dissolve, and obtain a PVP solution with a PVP concentration of 0.4.
[0100] 3) Fill two dispensing tubes with PVP and PI solutions respectively. Connect one end of each tube to the pressure controller and air compressor, and the other end to a T-junction. Connect the third port of the T-junction to a plastic blending tube, and connect the other end of the plastic blending tube to the dispensing needle. A schematic diagram and actual image of the printing equipment are shown below. Figure 2 As shown.
[0101] 4) Import the pre-written gcode into the 3D printer and start printing. Set the pressure of the adhesive tube at point A and point B to 316 kPa and 324 kPa respectively, and print 12 layers. At this time, the flow rates of the PI solution and PVP solution are 0.0009 and 0.0096 mL / min respectively, and the PI mass fraction of the obtained PVP / PI hydrogel material is 0.085. Then, set the pressure of the adhesive tube at point A and point B to 314 and 326 kPa respectively, and print 12 layers. At this time, the flow rates of the PI solution and PVP solution are 0.0030 and 0.0090 mL / min respectively, and the PI mass fraction of the obtained PVP / PI hydrogel material is 0.25. Finally, set the pressure of the adhesive tube at point A and point B to 312 and 328 kPa respectively, and print 12 layers. At this time, the flow rates of the PI solution and PVP solution are 0.0050 and 0.0100 mL / min respectively, and the PI mass fraction of the obtained PVP / PI hydrogel material is 0.333. As we know from the preceding description, a higher PI mass fraction results in a higher modulus and a lower equilibrium water absorption rate in the obtained PVP / PI hydrogel material. By adjusting the pressure applied to the A and B dispensing tubes during the printing process, the PI mass fraction of the PVP / PI hydrogel material can be changed, thereby obtaining a multilayer structure, such as... Figure 11 As shown.
[0102] 5) Place the printed sample in an oven and heat at 70℃ for 12 hours, then at 140℃ for 12 hours.
[0103] 6) Soak the dried sample in water for 34 hours to reach water absorption equilibrium.
[0104] like Figure 11 The top two images show the multilayer structure in the dry state, while the bottom image shows the multilayer structure after water absorption and swelling equilibrium. As previously demonstrated, structures with different PI mass fractions have different Young's moduli; therefore, the multilayer structure more closely resembles the gradient characteristics of real cartilage.
[0105] The extract of the dried PVP / PI hydrogel material obtained after solvent evaporation was subjected to cell proliferation and toxicity analysis (cell viability assay kit, CCK-8). The results are as follows: Figure 12 As shown, the extract was not significantly different from the control group, indicating that the PVP / PI hydrogel material had almost no cytotoxicity.
[0106] Although this application has been described with reference to preferred embodiments, various modifications can be made thereto and components can be replaced with equivalents without departing from the scope of this application. In particular, the technical features mentioned in the various embodiments can be combined in any manner, provided there is no structural conflict. This application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.
Claims
1. A hydrogel material, characterized in that, The hydrogel material comprises an A component and a B component, the A component is a polyimide; the B component is a polyvinylpyrrolidone, and the molecular chains of the A component and the B component are entangled to form a three-dimensional cross-linked network structure, wherein 0.025 < C A <0.375, C A is the mass fraction of the A component; and when the C A satisfies 0.025 < C A <0.375, the Young's modulus of the hydrogel material is 0.005-22.57 MPa, and the equilibrium water absorption of the hydrogel material is 127.8-725.0%.
2. A method of preparing a hydrogel material as claimed in claim 1, characterized in that The method comprises the following steps: (1) dissolving the A component and the B component in an organic solvent to obtain a mixed solution, wherein the ratio of the A component to the B component is controlled to obtain mixed solutions with different C A values; (2) heating the mixed solution to remove the organic solvent, so that the molecular chains of the A component and the B component are entangled to form a three-dimensional cross-linked network structure, thereby obtaining a hydrogel material.
3. The method of claim 2, wherein the hydrogel material is prepared by the method comprising the steps of: when the C A satisfies 0.025 < C A When the C satisfies 0.025 < C < 0.375, the Young's modulus of the hydrogel material is 0.005 ~ 22.57 MPa.
4. The method of claim 2, wherein the hydrogel material is prepared by the process of: When the C A When 0.025 < C A When 0.025 < C and < 0.375, the equilibrium water absorption of the hydrogel material is 127.8 to 725.0%.
5. The hydrogel material of claim 1 is used in artificial cartilage.
6. Use according to claim 5, characterized in that, The method comprises the following steps: (1) dissolving the A component and the B component in an organic solvent respectively to obtain an A solution and a B solution; (2) blending the A solution and the B solution in a 3D printing system, and performing 3D printing on the blended solution as ink, and heating to remove the organic solvent, thereby obtaining an artificial cartilage structure, wherein during the 3D printing process, the blending ratio of the A solution and the B solution is controlled to obtain blended solutions with different C A values.
7. Use according to claim 6, characterized in that, In the 3D printing process, the blending ratio of the A solution and the B solution is controlled by: controlling the flow rate of the A solution and the B solution into the 3D printing system to control the blending ratio of the blended solution.
8. Use according to claim 6, characterized in that, In the 3D printing process, the flow rate of the A solution and the B solution into the 3D printing system is controlled by: the A solution enters the 3D printing system through an A dispensing tube, the B solution enters the 3D printing system through a B dispensing tube, and the pressure applied to the A dispensing tube and the B dispensing tube is adjusted to control the flow rate of the A solution and the B solution.
9. Use according to claim 5, characterized in that, The method comprises the following steps: (1) dissolving the A component and the B component in an organic solvent to obtain a mixed solution, wherein the ratio of the A component to the B component is controlled to obtain mixed solutions with different C A values; (2) performing 3D printing on the mixed solution as ink, and heating to remove the organic solvent, thereby obtaining an artificial cartilage structure.
10. Use according to any one of claims 6 to 9, characterized in that, When the C A When 0.025 < C A When 0.025 < C and < 0.333, the compression modulus of the artificial cartilage structure is 0.08 to 4.36 MPa.
Citation Information
Patent Citations
Method for supplying inks for three-dimensional printing, and three-dimensional printing method using same
WO2017192004A1