Preparation method and application of bio-friendly and degradable composite material

Abstract

The invention belongs to but not limited to the technical field of degradable materials, and particularly relates to a preparation method of a bio-friendly and degradable composite material, which comprises the following steps: step 1, preparing carboxylated graphene oxide (GO-COOH); step 2, preparing polylipoic acid gel (PTA); step 3, preparing a lipoic acid-zinc composite material (PTAZ); step 4, preparing a lipoic acid-graphene composite material (PTAZ / GO); step 5, adjusting the mass ratio of GO-COOH to lipoic acid; step 6, carrying out post-treatment and performance testing on the material; step 7, characterizing and analyzing the material; and 8, carrying out application test and optimization. By combining lipoic acid with graphene, the conductivity of the material is remarkably improved, meanwhile, the degradability and mechanical performance of the material are kept, and the material is suitable for the fields of flexible electronics, sensors, biomedicine and the like.

Description

Technical Field

[0001] The present invention belongs to, but is not limited to, the technical field of degradable materials, and particularly relates to a preparation method and application of a bio-friendly and degradable composite material. Background Art

[0002] With the enhancement of environmental awareness and the improvement of the demand for sustainable development, the application of degradable materials in the fields of electronic devices, biomedicine, packaging, etc. has become increasingly widespread. However, existing degradable materials generally have the problem of insufficient conductivity, which limits their application in high-tech fields such as flexible electronics and sensors. Traditional conductive materials such as metals and carbon-based materials have excellent conductivity, but their biodegradability is poor and it is difficult to meet environmental protection requirements. Therefore, developing a composite material with both conductivity and degradability has become an important research direction in the field of materials science.

[0003] In recent years, graphene has been widely used in the preparation of composite materials due to its excellent conductivity, mechanical properties, and chemical stability. However, when used alone, graphene is difficult to effectively combine with degradable materials, and its dispersibility is poor, which easily leads to uneven material properties. As a natural degradable material, lipoic acid has good biocompatibility and self-assembly ability, but its conductivity is poor. By combining lipoic acid with graphene, the advantages of both can be fully utilized to prepare a composite material with both conductivity and degradability.

[0004] Currently, various preparation methods of graphene composite materials have been proposed, such as graphene composite materials prepared by chemical reduction methods or physical mixing methods. However, these methods often have problems such as complex processes, poor material dispersibility, and unstable conductivity. In addition, it is difficult to balance the conductivity and degradability of existing composite materials, and it is difficult to meet the requirements of high performance and environmental protection at the same time.

[0005] In view of the above analysis, the technical problems that urgently need to be solved in the prior art are: how to develop a lipoic acid-graphene composite material with both conductivity and degradability, and optimize its preparation process to improve the conductivity and stability of the material. Summary of the Invention

[0006] Aiming at the problems existing in the prior art, the present invention provides a preparation method of a bio-friendly and degradable composite material. By combining lipoic acid with graphene, the conductivity of the material is significantly improved, while maintaining its degradability and mechanical properties. The present invention adopts a simple preparation process to achieve the efficient preparation and wide application of the material.

[0007] The present invention is implemented as follows. A preparation method of a bio-friendly and degradable composite material includes: Step 1: Prepare a carboxylated graphene oxide (GO-COOH) solution with a specific concentration; Step 2: Prepare polythioctic acid gel (PTA); Step 3: Prepare a thioctic acid-zinc composite material (PTAZ); Step 4: Prepare a thioctic acid-graphene composite material (PTAZ / GO); Step 5: Adjust the mass ratio of GO-COOH to thioctic acid; Step 6: Post-treatment and performance testing of the materials; Step 7: Characterization and analysis of the materials; Step 8: Application testing and optimization.

[0008] Furthermore, the precursors for preparing carboxylated graphene oxide (GO-COOH) in Step 1 include graphene, carbon nanotubes, graphene oxide, sodium sulfate, calcium carbonate, sodium hydroxide, tannic acid, and monochloroacetic acid. The carboxylated graphene oxide (GO-COOH) solution needs to be ultrasonically treated in a cold water bath with an inorganic base first, then ultrasonically treated in an organic acid, and finally centrifuged and washed until neutral.

[0009] Furthermore, the molar ratios of the graphene solution, inorganic acid, and organic base for preparing carboxylated graphene oxide (GO-COOH) in Step 1 are 5:100:1, 5:100:10, 3:90:1, and 3:90:10.

[0010] Furthermore, the natural antioxidant acids for preparing polythioctic acid gel (PTA) in Step 2 include vitamin C (ascorbic acid), thioctic acid, and tannic acid, etc.: Mix the natural antioxidant acids with a solvent, place them in a reactor, slowly add a solubilizer to dissolve them. After the solution is transferred to a mold, let it stand at room temperature for a certain period of time, and finally form polythioctic acid gel (PTA). Special note: This process forms a certain structure in the solvent through intermolecular interactions, and the polymerization reaction may be achieved through natural evaporation of the solvent or other physical phenomena, thus avoiding energy waste caused by excessive polymerization reactions at high temperatures.

[0011] Furthermore, the method for preparing the thioctic acid-zinc composite material (PTAZ) in Step 3 includes: In a three-necked flask, add an appropriate amount of the solvent obtained in Step 2, and disperse ZnCl2 in the solvent. This process is carried out under ultrasonic treatment and stirring conditions to ensure uniform mixing. Subsequently, the solution is injected into a mold and left to stand at room temperature for a certain period of time to obtain the thioctic acid-zinc composite material (PTAZ). By adjusting the mass ratio of ZnCl2 to thioctic acid, composite materials with different properties can be obtained.

[0012] Furthermore, the method for preparing the lipoic acid-graphene composite material (PTAZ / GO) in Step 4 includes: adding the solvent obtained in Step 3 into a suitable reaction vessel, then adding one or more auxiliary chemical reagents, and fully mixing them through ultrasonic treatment and stirring. The finally obtained solution is left standing in a mold to form a composite material. Then, a small amount of the solution obtained in Step 1 is slowly added into the reaction vessel, stirred under appropriate conditions, and further chemical reagents are added. After mixing, it is injected into the mold and left standing until the reaction is completed.

[0013] Furthermore, in Step 6, the post-treatment of the material includes steps such as drying and heat treatment degradation to further optimize its mechanical properties and stability. The performance tests mainly include degradability tensile strength, antioxidant capacity, conductivity, etc.

[0014] Furthermore, in Step 7, the characterization and analysis of the material are carried out by methods such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and tensile testing.

[0015] Furthermore, in Step 8, the application tests include applying the composite material to specific scenarios, such as biomedical sensors, flexible electronics, environmental monitoring devices, etc. The key points of the tests include the actual performance of the material, long-term stability, and application effects under specific conditions.

[0016] Combined with the above technical solutions and the technical problems solved, the advantages and positive effects of the technical solution to be protected by the present invention are as follows: First, the present invention proposes a method for preparing a composite material based on lipoic acid and graphene. By combining lipoic acid with graphene, the conductivity of the material is significantly improved, while its degradability and mechanical properties are maintained. First, through the preparation of carboxylated graphene oxide (GO-COOH), the dispersibility of graphene and its binding ability with lipoic acid are enhanced. The carboxylation treatment of graphene not only improves its uniform distribution in the composite material but also enhances the interaction between its molecules and lipoic acid molecules, thus improving the overall performance of the material. Subsequently, through the self-assembly of lipoic acid to form polythioctic acid gel (PTA), the energy loss caused by high-temperature polymerization is avoided. This process is achieved through solvent evaporation, ensuring the formation of a stable gel structure of the material under mild conditions and avoiding the possible degradation or performance loss of the material during the traditional high-temperature polymerization process. Finally, by introducing ZnCl2 and GO-COOH, a lipoic acid-graphene composite material (PTAZ / GO) with excellent conductivity and degradability is prepared. The introduction of ZnCl2 further enhances the conductivity of the material, while the addition of GO-COOH ensures the mechanical strength and degradability of the material.

[0017] This composite material not only has excellent electrical conductivity, but also has good biocompatibility and degradability, and is suitable for fields such as flexible electronics, sensors, and biomedicine. By adjusting the mass ratio of GO-COOH to lipoic acid, the electrical conductivity and mechanical properties of the material can be further optimized to meet the requirements of different application scenarios. For example, in flexible electronic devices, this material can be used as a conductive layer to provide excellent electrical conductivity and flexibility; in the field of biomedicine, this material can be used to prepare degradable electronic sensors or drug delivery systems, with good biocompatibility and environmental friendliness.

[0018] Through reasonable material selection and processing steps, the present invention has achieved a double improvement in electrical conductivity and degradability, breaking through the trade-off between electrical conductivity and degradability of traditional materials. Although traditional conductive materials such as metals and carbon-based materials have excellent electrical conductivity, their biodegradability is poor and it is difficult to meet environmental protection requirements. While existing degradable materials have good biocompatibility and degradability, their electrical conductivity is generally insufficient and it is difficult to be applied in high-performance electronic devices. The present invention has successfully achieved a double improvement in electrical conductivity and degradability by combining lipoic acid with graphene, filling the technical gap in this field.

[0019] Second, as the creative auxiliary evidence of the claims of the present invention, it is also reflected in the following important aspects: (1) The expected benefits and commercial value after the transformation of the technical solution of the present invention are: The lipoic acid-graphene composite material of the present invention has broad commercial application potential due to its unique electrical conductivity and degradability, especially in high-value-added fields such as flexible electronics, sensors, and biomedicine. The expected benefits after transformation include the following aspects: 1. Flexible electronics field: This composite material can be used as a conductive material for flexible electronic components. With its excellent electrical conductivity and flexibility, it can be widely used in high-tech products such as touch screens and wearable devices, with extremely high commercial value. 2. Sensor field: Since this material has both electrical conductivity and degradability, it can be used as a sensitive material for sensors and is suitable for fields such as environmental monitoring and biosensing, with broad market prospects. 3. Biomedicine field: This material has good biocompatibility and degradability and can be used in biomedical sensors, drug delivery systems, etc., and is expected to significantly improve the safety of medical devices and the comfort of patients.

[0020] By combining with the relevant industrial chain, the composite material of the present invention can not only meet the market demand, but also significantly improve the added value of products, bringing long-term economic benefits to relevant enterprises.

[0021] (2) The technical solution of the present invention fills the domestic and foreign industry technical gaps: Existing degradable materials generally have deficiencies in conductivity, and existing conductive materials often struggle to balance degradability. Although there have been various studies on graphene composites at home and abroad, most have focused on optimizing single properties, such as improving conductivity or mechanical properties, while neglecting the overall enhancement of degradability. In this invention, by introducing lipoic acid to combine with graphene, for the first time, the simultaneous improvement of conductivity and degradability is achieved, and a simple preparation process is adopted, greatly simplifying the preparation process.

[0022] This technology fills the gap in the comprehensive performance of degradable materials in terms of conductivity and degradability at home and abroad, providing a new direction for the research and application of multifunctional composite materials.

[0023] (3) The technical solution of this invention solves the technical problems that people have been eager to solve but have never succeeded in: For a long time, researchers have been seeking a composite material that not only has excellent conductivity but also has degradability, which can meet the application requirements in fields such as flexible electronics, sensors, and biomedicine. However, traditional conductive materials are prone to breakage under high stress, and their degradability is difficult to meet environmental protection requirements. By combining lipoic acid and graphene, this invention effectively overcomes these technical problems and develops a composite material that integrates conductivity and degradability, successfully filling the gap in this field for many years.

[0024] (4) The technical solution of this invention overcomes the technical prejudice: The traditional view is that there is an inevitable trade-off between the conductivity and degradability of conductive materials, and pursuing high conductivity usually sacrifices the degradability of the material. This invention breaks through this technical prejudice. By reasonably designing the composite structure of lipoic acid and graphene, while maintaining high conductivity, the degradability of the material is significantly improved. This innovative design breaks the trade-off between traditional material properties and provides a new idea for the research and development of composite materials. Brief Description of the Drawings

[0025] Figure 1 is the sample preparation and processing flow chart provided by the embodiment of this invention; Figure 2 is the schematic diagram of the material microstructure characterization results of the material in Embodiment 1 provided by the embodiment of this invention; Figure 3 is the schematic diagram of the degradability test and tensile strength test results of the materials in Embodiments 1, 2, 3, and 4 provided by the embodiment of this invention; Figure 4 is the schematic diagram of the sensing mechanical property test results of the materials in Embodiments 1, 2, 3, and 4 provided by the embodiment of this invention; Figure 5Schematic diagram of the sensing sensitivity results of Embodiment Cases 1, 2, 3, and 4 provided by the embodiments of the present invention.

[0026] Figure 6 Schematic diagram of the biodegradability test results of the material in Embodiment Case 1 provided by the embodiments of the present invention. Detailed implementation manners

[0027] In order to make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0028] As Figure 1 shown, a simple preparation method of a biocompatible and biodegradable composite material provided by the embodiments of the present invention includes the following steps: Step 1, prepare carboxylated graphene oxide (GO-COOH); Step 2, prepare polythioctic acid gel (PTA); Step 3, prepare thioctic acid-zinc composite material (PTAZ); Step 4: Prepare thioctic acid-graphene composite material (PTAZ / GO); Step 5: Adjust the mass ratio of GO-COOH to thioctic acid; Step 6: Post-treatment and performance testing of the material; Step 7: Material characterization and analysis; Step 8: Application testing and optimization.

[0029] In the present invention, first, by preparing carboxylated graphene oxide (GO-COOH), the dispersibility of graphene and the binding ability with thioctic acid are enhanced. Subsequently, polythioctic acid gel (PTA) is formed by the self-assembly of thioctic acid, avoiding energy loss caused by high-temperature polymerization. Finally, by introducing ZnCl2 and GO-COOH, a thioctic acid-graphene composite material (PTAZ / GO) with excellent conductivity and biodegradability is prepared.

[0030] The present invention preferably selects 10 mL of rGO solution with a concentration of 2.0 mg / mL as the conductive medium, calcium carbonate as the inorganic base, ethanol as the solvent, and the mass ratio of the rGO solution to calcium carbonate is 5:1. The mixed system is ultrasonically treated in a cold water bath for 2 hours, and then 2.0 g of tannic acid is added, and ultrasonically treated for another 2 hours. The target product is obtained by centrifugal separation and washed with deionized water until neutral.

[0031] In this invention, 2 g of lipoic acid was preferentially placed in a 50 mL three-necked flask and dissolved in 2 mL of ethanol. The resulting solution was transferred to a mold and left to stand at room temperature for 12 hours to obtain polythioctic acid gel (PTA). Special note: The polymer molecular chains self-assembled in ethanol, and the polymerization reaction was achieved through the solvent evaporation process, avoiding the energy loss caused by high-temperature ring-opening polymerization.

[0032] In this invention, 2 g of lipoic acid and 2 mL of ethanol were successively added to a 50 mL three-necked flask. Subsequently, ZnCl2 (with a mass ratio of 1.0% of lipoic acid) was dispersed in 1 mL of ethanol, and after ultrasonic treatment for 20 minutes, it was added dropwise to the system under magnetic stirring. Finally, the solution was injected into a mold and left to stand at room temperature for 12 hours to prepare a lipoic acid-zinc composite material (PTAZ).

[0033] In this invention, 20 mg of a 5 mg / mL GO-COOH solution was slowly added to a 50 mL three-necked flask containing 2 g of lipoic acid. 1 mL of a 0.02 g / mL ZnCl2 solution was injected under magnetic stirring. After the mixture was cast into a mold and cooled to room temperature, a lipoic acid-graphene composite material (PTAZ / GO 1.0) was obtained. By fixing the mass ratio of GO-COOH to lipoic acid (2%), adjusting the molar ratio of tannic acid to calcium carbonate to 100:1 and 10:1, and adjusting the molar ratio of tannic acid to graphene oxide to 20:1 and 30:1. Materials of types PTAZ / GO 1.0, 2.0, and 4.0 were prepared using the same process respectively.

[0034] Lipoic acid (TA) was directly purchased from Adamas®beta company, reagent grade (99%). Zinc chloride (ZnCl2) was from Aladdin Industrial Corporation (China). All other reagents were from the CASMART platform (China).

[0035] Example 1 A preparation method of a bio-friendly and degradable composite material includes the following steps: (1) In a beaker containing 10 mL of a 2.0 mg / mL GO solution, 2.4 g of tannic acid was added. The mixed system was ultrasonically treated in a cold water bath for 2 hours. Subsequently, 2.0 g of calcium carbonate was added and ultrasonic treatment was continued for 2 hours. The target product was obtained by centrifugal separation and washed with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH); (2) 2 g of lipoic acid was placed in a 50 mL three-necked flask and dissolved in 2 mL of ethanol. The resulting solution was transferred to a mold and left to stand at room temperature for 12 hours to obtain polythioctic acid gel (PTA); (3) Add 2 g of lipoic acid and 2 mL of ethanol to a 50 mL three-necked flask in sequence. Subsequently, disperse ZnCl2 (mass ratio of 0.1% of TA) in 1 mL of ethanol, and after ultrasonic treatment for 20 minutes, add it dropwise to the system under magnetic stirring. Finally, inject the solution into a mold and let it stand at room temperature for 12 hours to obtain PTAZ; (4) In a three-necked flask containing 2 g of lipoic acid, slowly add 20 mg of a 5 mg / mL GO-COOH solution. Inject 1 mL of a 0.02 g / mL ZnCl2 solution under magnetic stirring. Pour the mixture into a mold and cool it to room temperature to obtain PTAZ / GO 1.0.

[0036] Example 2 A preparation method of a biocompatible and biodegradable composite material, comprising the following steps: (1) Add 2.4 g of calcium carbonate to a beaker containing 10 mL of a 2.0 mg / mL GO solution. Ultrasonically treat the mixed system in a cold water bath for 2 hours. Subsequently, add 2.0 g of tannic acid and continue ultrasonic treatment for 2 hours. Obtain the target product by centrifugal separation and wash it with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH); (2) Place 2 g of lipoic acid in a 50 mL three-necked flask, add 2 mL of ethanol to dissolve it. Transfer the obtained solution to a mold and let it stand at room temperature for 12 hours to obtain polythioctic acid gel (PTA); (3) Add 2 g of lipoic acid and 2 mL of ethanol to a 50 mL three-necked flask in sequence. Subsequently, disperse ZnCl2 (mass ratio of 1.0% of TA) in 1 mL of ethanol, and after ultrasonic treatment for 20 minutes, add it dropwise to the system under magnetic stirring. Finally, inject the solution into a mold and let it stand at room temperature for 12 hours to obtain PTAZ; (4) In a three-necked flask containing 2 g of lipoic acid, slowly add 40 mg of a 5 mg / mL GO-COOH solution. Inject 1 mL of a 0.02 g / mL ZnCl2 solution under magnetic stirring. Pour the mixture into a mold and cool it to room temperature to obtain PTAZ / GO 2.0.

[0037] Example 3 A preparation method of a biocompatible and biodegradable composite material, comprising the following steps: (1) Add 2.4 g of calcium carbonate to a beaker containing 10 mL of a 2.0 mg / mL GO solution. Ultrasonically treat the mixed system in a cold water bath for 2 hours. Subsequently, add 2.0 g of tannic acid and continue ultrasonic treatment for 2 hours. Obtain the target product by centrifugal separation and wash it with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH); (2) Place 2 g of lipoic acid in a 50 mL three-necked flask, and add 2 mL of ethanol to dissolve it. Transfer the resulting solution to a mold and let it stand at room temperature for 12 hours to obtain polythioctic acid gel (PTA); (3) Add 2 g of lipoic acid and 2 mL of ethanol to a 50 mL three-necked flask in sequence. Subsequently, disperse ZnCl2 (mass ratio 2.5% of TA) in 1 mL of ethanol, ultrasonic for 20 minutes, and then add it dropwise to the system under magnetic stirring. Finally, inject the solution into a mold and let it stand at room temperature for 12 hours to prepare PTAZ; (4) In a three-necked flask containing 2 g of lipoic acid, slowly add 80 mg of 5 mg / mL GO-COOH solution. Inject 1 mL of 0.02 g / mL ZnCl2 solution under magnetic stirring. Pour the mixture into a mold and cool it to room temperature to obtain PTAZ / GO 4.0.

[0038] Example 4 A method for preparing a biocompatible and biodegradable composite material, comprising the following steps: (1) Add 2.4 g of calcium carbonate to a beaker containing 10 mL of 2.0 mg / mL GO solution. Ultrasonically treat the mixed system in a cold water bath for 2 hours. Subsequently, add 2.0 g of tannic acid and continue ultrasonic treatment for 2 hours. Obtain the target product by centrifugal separation and wash it with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH); (2) Place 2 g of lipoic acid in a 50 mL three-necked flask, and add 2 mL of ethanol to dissolve it. Transfer the resulting solution to a mold and let it stand at room temperature for 12 hours to obtain polythioctic acid gel (PTA); (3) Add 2 g of lipoic acid and 2 mL of ethanol to a 50 mL three-necked flask in sequence. Subsequently, disperse ZnCl2 (mass ratio 5.0% of TA) in 1 mL of ethanol, ultrasonic for 20 minutes, and then add it dropwise to the system under magnetic stirring. Finally, inject the solution into a mold and let it stand at room temperature for 12 hours to prepare PTAZ; (4) In a three-necked flask containing 2 g of lipoic acid, slowly add 100 mg of 5 mg / mL GO-COOH solution. Inject 1 mL of 0.02 g / mL ZnCl2 solution under magnetic stirring. Pour the mixture into a mold and cool it to room temperature to obtain PTAZ / GO 5.0.

[0039] These examples demonstrate the diverse applications of lipoic acid-graphene composites in the fields of flexible electronics, sensors, biomedicine, etc. according to the claims. By adjusting the mass ratio of GO-COOH to lipoic acid, applications in different environmental factors can be achieved to meet various practical application requirements.

[0040] The present invention provides a method for preparing a bio-friendly and degradable composite material. Through reasonable material selection and processing steps, the composite material has excellent electrical conductivity and degradability. This method mainly realizes the multiple functions of the material by regulating the internal structure and external morphology of the material, and has broad application prospects, especially in the fields of flexible electronics, sensors, biomedicine, etc.

[0041] The present invention provides a method for preparing a bio-friendly and degradable composite material. Through reasonable material selection and processing steps, the composite material has excellent electrical conductivity and degradability. This method mainly realizes the multiple functions of the material by regulating the internal structure and external morphology of the material, and has broad application prospects, especially in the fields of flexible electronics, sensors, biomedicine, etc.

[0042] 1. Preparation of carboxylated graphene oxide (GO-COOH): In the first step, the preparation of carboxylated graphene oxide (GO-COOH) enhances the dispersibility of graphene and its binding ability with lipoic acid. This step ensures the uniform distribution of graphene in the composite material and lays a foundation for the subsequent preparation of the composite material.

[0043] 2. Preparation of polythioctic acid gel (PTA): In the second step, polythioctic acid gel (PTA) is formed by the self-assembly of lipoic acid, avoiding the energy loss caused by high-temperature polymerization. This step provides a good base material for the subsequent preparation of the composite material.

[0044] 3. Preparation of lipoic acid-graphene composite material (PTAZ / GO): In the third step, by introducing ZnCl2 and GO-COOH, a lipoic acid-graphene composite material (PTAZ / GO) with excellent electrical conductivity and degradability is prepared. This step realizes the simultaneous improvement of electrical conductivity and degradability by regulating the internal structure of the material.

[0045] Through this series of steps, the preparation method of the present invention ensures that the lipoic acid-graphene composite material has excellent electrical conductivity and degradability, and can prepare complex shapes that meet the actual application requirements through a simple preparation process. This method not only simplifies the preparation process of the composite material, but also greatly improves the application breadth and stability of the material.

[0046] Example 1: Lipoic acid-graphene composite material for flexible electronic devices 1. Preparation of carboxylated graphene oxide (GO-COOH): Add 2.4 g of calcium carbonate to a beaker containing 10 mL of 2.0 mg / mL GO solution. The mixed system is ultrasonically treated in a cold water bath for 2 hours. Then add 2.0 g of tannic acid and continue ultrasonically treating for 2 hours. The target product is obtained by centrifugal separation and washed with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH).

[0047] 2. Preparation of polythioctic acid gel (PTA): Place 2 g of thioctic acid in a 50 mL three-necked flask, add 2 mL of ethanol to dissolve. The resulting solution is transferred to a mold and left standing at room temperature for 12 hours to obtain polythioctic acid gel (PTA).

[0048] 3. Preparation of thioctic acid-graphene composite material (PTAZ / GO): Add 2 g of thioctic acid and 2 mL of ethanol to a 50 mL three-necked flask in sequence. Then disperse ZnCl2 (0.1% of the mass ratio of TA) in 1 mL of ethanol, ultrasonically treat for 20 minutes, and then add it dropwise to the system under magnetic stirring. The final solution is poured into a mold and left standing at room temperature for 12 hours to prepare PTAZ.

[0049] 4. Application of the composite material: Apply the PTAZ / GO 1.0 material to the conductive layer of a flexible electronic device and test its conductivity and flexibility.

[0050] Application effect: The flexible electronic device made of this thioctic acid-graphene composite material has excellent conductivity and flexibility, can be used for a long time, and has good biocompatibility and degradability, making it suitable for wearable health devices.

[0051] Example 2: Thioctic acid-graphene composite material for sensors 1. Preparation of carboxylated graphene oxide (GO-COOH): Add 2.4 g of calcium carbonate to a beaker containing 10 mL of 2.0 mg / mL GO solution. The mixed system is ultrasonically treated in a cold water bath for 2 hours. Then add 2.0 g of tannic acid and continue ultrasonically treating for 2 hours. The target product is obtained by centrifugal separation and washed with deionized water until neutral to obtain carboxylated graphene oxide (GO-COOH).

[0052] 2. Preparation of polythioctic acid gel (PTA): Place 2 g of thioctic acid in a 50 mL three-necked flask, add 2 mL of ethanol to dissolve. The resulting solution is transferred to a mold and left standing at room temperature for 12 hours to obtain polythioctic acid gel (PTA).

[0053] 3. Preparation of thioctic acid-graphene composite material (PTAZ / GO): Add 2 g of thioctic acid and 2 mL of ethanol into a 50 mL three-necked flask in sequence. Subsequently, disperse ZnCl2 (with a mass ratio of 1.0% of TA) in 1 mL of ethanol, ultrasonic for 20 minutes, and then add it dropwise into the system under magnetic stirring. Finally, inject the solution into a mold and let it stand at room temperature for 12 hours to obtain PTAZ.

[0054] 4. Application of the composite material: Apply the PTAZ / GO 2.0 material to the sensitive layer of the sensor and test its conductivity and sensitivity.

[0055] Application effect: The sensor made of this thioctic acid-graphene composite material has excellent conductivity and sensitivity, can accurately detect environmental parameters, and has good biocompatibility and degradability, making it suitable for environmental monitoring and biosensing fields.

[0056] II. Evidence related to the technical effects obtained in the embodiments of the present invention.

[0057] In the description of the present invention, unless otherwise specified, "a plurality of" means two or more; the orientation or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", "front end", "rear end", "head", "tail", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be construed as a limitation of the present invention. In addition, the terms "first", "second", "third", etc. are only used for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0058] As mentioned above, the above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be covered by the protection scope of the present invention.

Claims

1. A method for preparing a biofriendly, degradable composite material, characterized in that: include: Step 1, preparing carboxylated graphene oxide (GO-COOH); Step 2, preparing polylipoic acid gel (PTA); Step 3, preparing lipoic acid-zinc composite material (PTAZ); Step 4: preparing lipoic acid-graphene composite material (PTAZ / GO); Step 5: Adjust the mass ratio of GO-COOH to lipoic acid; Step 6: Material post-processing and performance testing; Step 7: Material characterization and analysis; Step 8: Application testing and optimization.

2. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: The precursors for preparing carboxylated graphene oxide (GO-COOH) in step 1 include graphene, carbon nanotubes, graphene oxide, sodium aminosulfate, calcium carbonate, sodium hydroxide, tannic acid, and monochloroacetic acid. The carboxylated graphene oxide (GO-COOH) solution needs to be firstly ultrasonically treated in a cold water bath in an inorganic base, then ultrasonically treated in an organic acid, and finally centrifuged and washed to neutrality.

3. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: In step 1, the molar ratios of the graphene solution, the inorganic acid and the organic base for preparing carboxylated graphene oxide (GO-COOH) are 5:100:1, 5:100:10, 3:90:1 and 3:90:

10.

4. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: The natural antioxidant acids used to prepare polylipoic acid gel (PTA) in step 2 include vitamin C (ascorbic acid), lipoic acid and tannic acid, etc.: the natural antioxidant acids are mixed with a solvent, placed in a reactor, and a solvent is slowly added to dissolve the mixture. After the solution is transferred to a mold, it is allowed to stand at room temperature for a period of time to finally form polylipoic acid gel (PTA). Special note: This process forms a certain structure in the solvent through intermolecular interactions, and the polymerization reaction may be achieved through natural evaporation of the solvent or other physical phenomena, thereby avoiding energy waste caused by excessive polymerization reactions triggered at high temperatures.

5. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: The method for preparing the lipoic acid-zinc composite material (PTAZ) in step 3 includes: adding an appropriate amount of the solvent obtained in step 2 to a three-necked flask, and dispersing ZnCl2 in the solvent. This process is carried out under the conditions of ultrasonic treatment and stirring to ensure uniform mixing. Subsequently, the solution is injected into a mold and allowed to stand at room temperature for a certain period of time to obtain a lipoic acid-zinc composite material (PTAZ). By adjusting the mass ratio of ZnCl2 to lipoic acid, composite materials with different properties can be obtained.

6. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: The method for preparing the lipoic acid-graphene composite material (PTAZ / GO) in step 4 includes: adding the solvent obtained in step 3 to an appropriate reaction container, then adding one or more auxiliary chemical reagents, and mixing them thoroughly by ultrasonic treatment and stirring. The resulting solution is allowed to stand in a mold to form a composite material. Then, a small amount of the solution obtained in step 1 is slowly added to the reaction container, stirred under appropriate conditions and further chemical reagents are added, mixed, injected into the mold, and allowed to stand until the reaction is completed.

7. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: In step six, the post-processing of the material includes drying, heat treatment and degradation steps to further optimize its mechanical properties and stability. Performance tests mainly include degradability, tensile strength, antioxidant capacity, conductivity, etc.

8. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: In step seven, the characterization and analysis of the materials include scanning electron microscopy (SEM), infrared spectroscopy (FTIR), tensile testing and other methods.

9. The method for preparing the bio-friendly, degradable composite material according to claim 1, characterized in that: In step eight, application testing involves applying composite materials to specific scenarios, such as biomedical sensors, flexible electronics, environmental monitoring equipment, etc. The focus of the test includes the actual performance of the material, long-term stability, and application effect under specific conditions.

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