Myogenic mechanically adaptive stiffening ankle anti-twist hydrogel patch and preparation method thereof

Abstract

The application discloses a myogenic mechanics self-adapting rigidness-increasing ankle anti-twist hydrogel patch and a preparation method thereof, and specifically implements the following steps: step 1, preparing a basic mixed solution; step 2, preparing a mixed cross-linking solution through the basic mixed solution; and step 3, preparing the myogenic mechanics self-adapting rigidness-increasing ankle anti-twist hydrogel patch through the mixed cross-linking solution. When the ankle is not obviously twisted, the hydrogel patch keeps the characteristics of softness and skin adhesion, does not bind the normal flexion, extension and rotation of the ankle joint, can closely adhere to the skin, and guarantees the comfort during long-time wearing. When the ankle is suddenly twisted, the modulus of the hydrogel is instantaneously increased, the rigidity is rapidly enhanced, a rigid protective support is formed in a very short time, the ankle is effectively limited from being excessively twisted, and the instantaneous impact force caused by the twisting deformation is buffered and resisted.

Description

Technical Field

[0001] This invention belongs to the field of protective equipment technology, specifically relating to a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, and also to a method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch. Background Technology

[0002] In high-altitude skydiving, extreme sports, and high-intensity jumping sports such as track and field and basketball, the lower limbs, especially the ankle joint, are subjected to instantaneous and intense impact and dynamic load upon landing. This type of impact is characterized by high strain rate, instantaneous high load, and variable direction, easily causing acute sprains such as inversion, eversion, and excessive flexion and extension of the ankle joint, severely affecting athletic performance and limb health. Traditional ankle protection equipment mostly uses rigid support; however, while rigid braces offer strong stability, they suffer from poor fit, significantly restrict movement, and are unable to adapt to the natural movement posture of the joint, failing to provide sufficient precise fit in a timely manner, reducing effective external support, and affecting ankle joint stability.

[0003] Therefore, developing a biomimetic muscle hydrogel material that is soft and skin-friendly under low loads, exhibits a significant increase in modulus and rapid enhancement in stiffness under high impact instantaneous loads is of great practical significance and has broad application prospects for achieving dynamic adaptive anti-torsion of the ankle joint and improving the safety and comfort of high-altitude sports and jumping sports. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, which solves the problems of poor fit and significant restriction of ankle joint movement in existing ankle joint protective equipment.

[0005] Another object of the present invention is to provide a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0006] The technical solution adopted in this invention is a method for preparing a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, which is implemented according to the following steps: Step 1: Prepare the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions.

[0007] The invention is further characterized by: The specific process of step 1 is as follows: Step 1.1: Pour ultrapure water into a beaker and place the beaker in a constant temperature water bath. Turn on the digital display magnetic stirrer, slowly add silk fibroin and stir continuously until the silk fibroin is completely dissolved to form a transparent and uniform silk fibroin solution. Step 1.2: In the silk fibroin solution, carboxymethyl chitosan and purified NIPAM-HEMA copolymer are added sequentially. The water bath temperature is maintained and stirring is continued until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. Step 1.3: Add sodium hyaluronate and phenoxyethanol to mixed solution A, and continue stirring to ensure uniform dispersion, thus obtaining the basic mixed solution.

[0008] In steps 1.1 to 1.3, the mass ratio of ultrapure water, silk fibroin, carboxymethyl chitosan, purified NIPAM-HEMA copolymer, sodium hyaluronate, and phenoxyethanol is 3988~7976:150~250:250~450:175~350:80~120:1.

[0009] In step 1.1, the temperature of the constant temperature water bath is 45℃~55℃, and the stirring speed is 200r / min~350r / min; In step 1.2, the stirring speed is 100 r / min to 250 r / min; In step 1.3, the stirring speed is 100 r / min to 250 r / min, and the stirring time is 25 min to 50 min.

[0010] In step 1.2, the method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide and hydroxyethyl methacrylate in a molar ratio of 1:1 to 1.5 were fully dissolved in deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 25 to 30 minutes. Azobisisobutyronitrile was then added to the reaction mixture, and polymerization was carried out at 25°C to 60°C for 4 to 8 hours. After the polymerization was completed, the reaction system was quickly placed in an ice-water bath at 4°C to 8°C to terminate the polymerization and obtain NIPAM-HEMA copolymer containing impurities. The obtained NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, and then dialyzed with deionized water for 48 to 72 hours. After the dialyz was completed, the purified NIPAM-HEMA copolymer was obtained. In the reaction mixture, the sum of the mass fractions of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 5%~15%, the mass fraction of deionized water is 85%~95%, and the sum of the mass percentages of the above components is 100%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) to hydroxyethyl methacrylate (HEMA) is 5~15:100.

[0011] The specific process of step 2 is as follows: Step 2.1: Add graphene oxide to the basic mixed solution, turn on the ultrasonic disperser for ultrasonic dispersion, and stir magnetically at the same time to obtain mixed solution B; Step 2.2: Add polyethylene glycol diacrylate and N,N-methylenebisacrylamide to mixed solution B, stir until completely dissolved, then add ammonium persulfate initiator and stir, then slowly add lanthanum chloride and stir, then slowly add phthalaldehyde and stir to obtain a mixed crosslinking solution.

[0012] In steps 2.1 to 2.2, the mass ratio of graphene oxide, polyethylene glycol diacrylate, N,N-methylenebisacrylamide, ammonium persulfate, lanthanum chloride, and phthalaldehyde is 1:26~90:0.6~2:1.6~5:16~40:1~3. The mass ratio of graphene oxide to phenoxyethanol is 1:0.375~1.

[0013] The specific process of step 3 is as follows: slowly pour the mixed crosslinking solution into the silicone rubber mold, place the filled silicone rubber mold into a constant temperature water bath for constant temperature polymerization reaction, after the polymerization reaction is completed, remove the silicone rubber mold and let it cool naturally to room temperature, after cooling, a semi-finished hydrogel is obtained, slowly remove the semi-finished hydrogel from the silicone rubber mold, rinse the surface with ultrapure water to completely remove the unreacted residual reagents on the surface, place the rinsed semi-finished hydrogel in a constant temperature and humidity chamber for curing, and obtain a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0014] The isothermal polymerization reaction temperature is 65℃~80℃, the isothermal polymerization reaction time is 2.5h~5h, the curing temperature is 25℃~37℃, the curing humidity is 65%~75%, and the curing time is 24h~36h.

[0015] Another technical solution adopted in this invention is a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, which is prepared using the above-mentioned preparation method.

[0016] The beneficial effects of this invention are: (1) The preparation method of the myogenic mechanical adaptive stiffening ankle anti-twist hydrogel patch of the present invention uses a biomimetic design of a synergistic cross-linking network of ions, covalent and dynamic Schiff base bonds. It uses the deformation law of human skeletal muscle under force as a biomimetic prototype to replicate the dynamic characteristics of muscle fibers entangled and contracted and hardened when under force. Under the condition of ankle twisting, deformation is stiffening and stiffening plays a protective role. (2) The myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch prepared by the method of the present invention maintains the soft and skin-friendly properties of the hydrogel when there is no obvious twisting of the ankle and no significant deformation of the hydrogel during daily low-load activities. It does not restrict the normal flexion, extension and rotation of the ankle joint, but can closely fit the skin to ensure the comfort of wearing for a long time. When the ankle suddenly twists and the hydrogel is subjected to force and undergoes instantaneous deformation, the hydrogel modulus increases instantaneously and the stiffness increases rapidly. It forms a rigid protective support in a very short time, effectively limiting excessive twisting of the ankle, buffering and resisting the instantaneous impact force brought about by twisting deformation, and avoiding inversion, eversion and other injuries caused by excessive twisting amplitude and uneven instantaneous force on the ankle joint from the source. It greatly improves the timeliness and reliability of protection in ankle twisting scenarios. Attached Figure Description

[0017] Figure 1 The results show the compressive strength of the myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch obtained in Embodiment 1 of the present invention under different loading speeds. Detailed Implementation

[0018] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0019] The preparation method of the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch of the present invention comprises the following steps: Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour ultrapure water into a beaker and place the beaker in a constant temperature water bath at 45℃~55℃. Turn on the digital display magnetic stirrer and adjust the speed to 200r / min~350r / min. Slowly add silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, carboxymethyl chitosan and purified NIPAM-HEMA copolymer are added sequentially. The water bath temperature is maintained at 45℃~55℃, and the mixture is stirred at 100r / min~250r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) in a molar ratio of 1:1 to 1.5 were thoroughly dissolved in 100 ml of deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 25 to 30 minutes to thoroughly remove dissolved oxygen and prevent oxygen from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator, and the reaction was carried out at 25°C. The polymerization reaction was carried out at 60℃ for 4-8 hours. After the polymerization was completed, the reaction system was quickly cooled in an ice-water bath at 4-8℃ to terminate the polymerization reaction, resulting in a NIPAM-HEMA copolymer containing impurities. The NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, and then with deionized water for 48-72 hours to remove small molecule monomers and initiator fragments. After dialyzing, the purified NIPAM-HEMA copolymer was obtained. The total mass fraction of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) in the reaction mixture was 5-15%, the mass fraction of deionized water was 85-95%, and the total mass percentage of the above components was 100%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 5~15:100. The dialysis bags used in the dialysis process have a molecular weight cutoff of MWCO: 3500 Da~14000 Da; Step 1.3: Add sodium hyaluronate and phenoxyethanol to mixed solution A, adjust the stirring speed to 100 r / min~250 r / min, and continue stirring for 25 min~50 min to ensure uniform dispersion and obtain the basic mixed solution; The mass ratio of ultrapure water, silk fibroin, carboxymethyl chitosan, purified NIPAM-HEMA copolymer, sodium hyaluronate, and phenoxyethanol is 3988~7976:150~250:250~450:175~350:80~120:1. Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add graphene oxide (GO) to the basic mixed solution, turn on the ultrasonic disperser with a power of 200W~300W, and ultrasonically disperse for 30min~45min. At the same time, continue to magnetically stir at a speed of 200r / min~500r / min to make the graphene oxide sheets uniformly dispersed in the solution and avoid agglomeration, so as to obtain mixed solution B. Step 2.2: Add polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 200 rpm to 500 rpm for 20 to 35 minutes until completely dissolved. Then add ammonium persulfate (APS) initiator and stir for 20 to 30 minutes. Slowly add lanthanum chloride (LaCl3) and stir for 25 to 30 minutes to allow the LaCl3 to dissolve. 3+ The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the initial skeletal structure of muscle fibers. Then, phthalaldehyde (OPA) is slowly added dropwise and stirred for 20 to 30 minutes to allow phthalaldehyde to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links ionicly and covalently to obtain a mixed cross-linking solution. The mass ratio of graphene oxide, polyethylene glycol diacrylate, N,N-methylenebisacrylamide, ammonium persulfate, lanthanum chloride, and phthalaldehyde is 1:26~90:0.6~2:1.6~5:16~40:1~3. The mass ratio of graphene oxide to phenoxyethanol is 1:0.375~1; Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The specific process is as follows: The mixed crosslinking solution is slowly poured into a silicone rubber mold (available commercially available; silicone rubber molds are a current technology). The filled silicone rubber mold is then placed in a constant temperature water bath at 65℃~80℃ for 2.5h~5h. This allows the purified NIPAM-HEMA copolymer to fully polymerize, polyethylene glycol diacrylate to complete covalent crosslinking, and the ionic crosslinking network and dynamic Schiff base bond crosslinking network to be further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle, ensuring the hydrogel's mechanical properties. With uniform performance, after the polymerization reaction is completed, the silicone rubber mold is removed and allowed to cool naturally to room temperature. After cooling, a semi-finished hydrogel is obtained. The semi-finished hydrogel is slowly removed from the silicone rubber mold and the surface is rinsed with ultrapure water 4-5 times to completely remove any unreacted residual reagents. The rinsed semi-finished hydrogel is then placed in a constant temperature and humidity chamber at a temperature of 25℃~37℃ and a humidity of 65%~75% for 24h~36h to further stabilize the cross-linked network, resulting in a water-based, mechanically adaptive, stiffening ankle anti-torsion hydrogel patch.

[0020] The water-based, muscle-derived, mechanically adaptive, stiffening ankle anti-torsion hydrogel patch prepared by the method of this invention can adapt to the dynamic needs of ankle movement. During daily low-load activities, when there is no significant ankle twisting and the hydrogel does not undergo significant deformation, the dynamic Schiff base bonds within the network are in a loose state, and the ionic cross-linking bonds are lightly bound. The biomimetic muscle fiber skeleton composed of carboxymethyl chitosan and silk fibroin is loose and relaxed, perfectly simulating the relaxed state of skeletal muscle. This allows the hydrogel to maintain its soft and skin-friendly properties, neither restricting the normal flexion, extension, and rotation of the ankle joint, nor hindering its close contact with the skin, ensuring comfort during prolonged wear. When a sudden ankle twist occurs and the hydrogel undergoes instantaneous deformation under stress, the protective mechanism is quickly activated and responds instantly. The deformation force is transmitted through graphene oxide. The force is rapidly conducted into the hydrogel (graphene oxide's excellent force conduction properties enable instantaneous, full-domain force transmission), analogous to the dynamic changes of muscle fibers when subjected to force in human skeletal muscle. The biomimetic muscle fiber skeleton rapidly entangles and tightly arranges itself with deformation. Simultaneously, dynamic Schiff base bonds rapidly recombine, ionic cross-linking bonds tightly bind, and covalent cross-linking networks provide stable support. The three work together to instantly increase the hydrogel's modulus and rapidly enhance its stiffness, forming rigid protective support in a very short time. This effectively limits excessive ankle twisting, buffers and resists the instantaneous impact force caused by twisting deformation, and prevents ankle joint injuries such as inversion and eversion caused by excessive twisting amplitude and uneven instantaneous force from the source. This significantly improves the timeliness and reliability of protection in ankle twisting scenarios.

[0021] The method of this invention uses carboxymethyl chitosan and silk fibroin as the main materials, combined with graphene oxide and lanthanum chloride crosslinking agent. Carboxymethyl chitosan and silk fibroin accurately simulate the structure of skeletal muscle fibers, providing a structural basis for biomimetic anti-torsion. The reversible ionic crosslinking bond formed by lanthanum chloride and carboxymethyl chitosan, and the dynamic Schiff base bond formed by phthalaldehyde and silk fibroin, work together in a covalent crosslinking network to further amplify the linkage effect of deformation, entanglement and stiffness enhancement, ensuring that the hydrogel responds faster to ankle torsional deformation and provides stronger support stability, achieving a dual improvement in comfort and protection, and providing a new biomimetic material support for ankle protection.

[0022] Example 1 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 80mL of ultrapure water into a beaker and place the beaker in a 45℃ constant temperature water bath. Turn on the digital display magnetic stirrer, adjust the speed to 200r / min, slowly add 2.5g of silk fibroin and stir continuously until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 4.5g of carboxymethyl chitosan and 3.5g of purified NIPAM-HEMA copolymer in sequence, maintain the water bath temperature at 45℃, and continue stirring at 100r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide and hydroxyethyl methacrylate in a molar ratio of 1:1 were fully dissolved in 100 ml of deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 25 min. Azobisisobutyronitrile was then added to the reaction mixture, and polymerization was carried out at 25 °C for 8 h. After the polymerization was completed, the reaction system was quickly placed in an ice-water bath at 4 °C to cool and terminate the polymerization, resulting in a NIPAM-HEMA copolymer containing impurities. The NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 h, and then with deionized water for 48 h. After the dialyz was completed, the purified NIPAM-HEMA copolymer was obtained. In the reaction mixture, the sum of the mass fractions of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 15%, and the mass fraction of deionized water is 85%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 15:100. The dialysis bag used in the dialysis has a molecular weight cutoff of MWCO: 3500 Da; Step 1.3: Add 1.2g of sodium hyaluronate and 0.01g of phenoxyethanol to mixed solution A, adjust the stirring speed to 100r / min, and continue stirring for 25min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.01g of graphene oxide (GO) to the basic mixed solution, turn on the high-power ultrasonic disperser with a power of 300W, and ultrasonically disperse for 30min while maintaining magnetic stirring at 200r / min to make the graphene oxide sheets uniformly dispersed in the solution and avoid agglomeration, thus obtaining mixed solution B. Step 2.2: Add 0.9 g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.02 g of N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 200 r / min for 20 min until completely dissolved. Then add 0.05 g of ammonium persulfate (APS) initiator, stir for 20 min, and slowly add 0.4 g of lanthanum chloride (LaCl3), maintaining the stirring speed, and stir for 25 min to allow the La... 3+ The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.03 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 20 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links ionicly and covalently to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The mixed crosslinking solution was slowly poured into a silicone rubber mold. The filled silicone rubber mold was then placed in an 80°C constant temperature water bath for 2.5 hours to allow NIPAM-HEMA to fully polymerize and PEGDA to complete covalent crosslinking. The ionic crosslinking network and the dynamic Schiff base bond crosslinking network were further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle, ensuring uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and rinsed four times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was then placed in a 37°C, 75% humidity constant temperature and humidity chamber for 36 hours to further stabilize the crosslinking network, resulting in a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0023] Example 2 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 85mL of ultrapure water into a beaker and place the beaker in a 55℃ constant temperature water bath. Turn on the digital display magnetic stirrer and adjust the speed to 350r / min. Slowly add 3.5g of silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 6.5g of carboxymethyl chitosan and 5.5g of purified N-isopropylacrylamide-hydroxyethyl methacrylate copolymer (NIPAM-HEMA copolymer) monomer in sequence. Maintain a water bath temperature of 55°C and continue stirring at 250r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) were dissolved in 100 ml of deionized water at a molar ratio of 1:1.5 to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 30 min to thoroughly remove dissolved oxygen and prevent it from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator, and the polymerization reaction was carried out at 60 °C for 4 h. After the polymerization reaction was completed, the reaction system was quickly placed in an ice-water bath at 8 °C to cool and terminate the polymerization. The reaction yielded a NIPAM-HEMA copolymer containing impurities. This NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, followed by dialyzed with deionized water for 72 hours to remove small molecule monomers and initiator fragments. After dialysis, the purified NIPAM-HEMA copolymer was obtained. The reaction mixture contained 5% N-isopropylacrylamide (NIPAM) and 95% hydroxyethyl methacrylate (HEMA) by mass, and the total mass percentage of the above components was 100%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 5:100. The dialysis bag used in the dialysis had a molecular weight cutoff of MWCO: 14000 Da; Step 1.3: Add 1.8g of sodium hyaluronate and 0.02g of phenoxyethanol to mixed solution A, stir at 100r / min, and continue stirring for 50min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.05g of graphene oxide (GO) to the basic mixed solution, turn on a 200W high-power ultrasonic disperser, ultrasonically disperse for 45min, and simultaneously maintain magnetic stirring at 300r / min to ensure that the GO sheets are uniformly dispersed in the solution and avoid agglomeration, thus obtaining mixed solution B. Step 2.2: Add 1.3g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.03g of N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 300 rpm for 35 min until completely dissolved. Then add 0.08g of ammonium persulfate (APS) initiator, stir for 30 min, and slowly add 0.8g of lanthanum chloride (LaCl3) while maintaining the stirring speed for 30 min, so that La... 3+The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.05 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 30 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links with ionic and covalent cross-linking to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The mixed crosslinking solution was slowly poured into a silicone rubber mold. The filled silicone rubber mold was then placed in an 80°C constant temperature water bath for 5 hours to allow NIPAM-HEMA to fully polymerize and PEGDA to complete covalent crosslinking. The ionic crosslinking network and the dynamic Schiff base bond crosslinking network were further stabilized to form a complete three-dimensional network structure, accurately simulating the fiber network of skeletal muscle and ensuring uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and rinsed five times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was then placed in a 37°C, 75% humidity constant temperature and humidity chamber for 24 hours to further stabilize the crosslinking network, ultimately yielding a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0024] Example 3 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 80mL of ultrapure water into a beaker and place the beaker in a 55℃ constant temperature water bath. Turn on the digital display magnetic stirrer and adjust the speed to 300r / min. Slowly add 3.0g of silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 6.0g of carboxymethyl chitosan and 4.0g of purified N-isopropylacrylamide-hydroxyethyl methacrylate copolymer (NIPAM-HEMA copolymer) monomer in sequence. Maintain a water bath temperature of 45°C and continue stirring at a speed of 250r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) in a 1:1 molar ratio were thoroughly dissolved in 100 ml of deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 30 min to thoroughly remove dissolved oxygen and prevent it from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator, and the polymerization reaction was carried out at 40 °C for 6 h. After the polymerization reaction was completed, the reaction system was quickly placed at 6 °C. The polymerization reaction was terminated by cooling in an ice-water bath, resulting in a NIPAM-HEMA copolymer containing impurities. This NIPAM-HEMA copolymer containing impurities was dialyzed against methanol for 24 hours, followed by dialyzed against deionized water for 60 hours to remove small monomer molecules and initiator fragments. After dialysis, the purified NIPAM-HEMA copolymer was obtained. The reaction mixture contained 10% N-isopropylacrylamide (NIPAM) and 90% deionized water by mass. The ratio of the amount of azobisisobutyronitrile (AIBN) to the total amount of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 10:100. The dialysis bag used in the dialysis has a molecular weight cutoff of MWCO: 10000 Da; Step 1.3: Add 1.5g of sodium hyaluronate and 0.015g of phenoxyethanol to mixed solution A, stir at 250r / min, and continue stirring for 50min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.02g of graphene oxide (GO) to the basic mixed solution, turn on the high-power ultrasonic disperser with a power of 300W, and ultrasonically disperse for 30min. At the same time, continue to magnetically stir at a speed of 400r / min to make the GO sheets uniformly dispersed in the solution and avoid agglomeration, so as to obtain mixed solution B. Step 2.2: Add 1.0 g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.03 g of N,N-methylenebisacrylamide (MBA) to mixed solution B. Stir at 400 rpm for 35 min until completely dissolved. Then add 0.06 g of ammonium persulfate (APS) initiator and stir for 30 min. Slowly add 0.6 g of lanthanum chloride (LaCl3) while maintaining the stirring speed and stirring for a certain period of time, allowing the LaCl3 to dissolve completely. 3+The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.03 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 30 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links with ionic and covalent cross-linking to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The mixed crosslinking solution was slowly poured into a silicone rubber mold. The filled silicone rubber mold was placed in a constant temperature water bath at 70°C and the polymerization reaction was carried out at a constant temperature for 5 hours to allow NIPAM-HEMA to fully polymerize, PEGDA to complete covalent crosslinking, and the ionic crosslinking network and dynamic Schiff base bond crosslinking network to be further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle and ensures uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and the surface was rinsed 5 times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was then placed in a constant temperature and humidity chamber at 37°C and 75% humidity for 36 hours to further stabilize the crosslinking network, resulting in a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0025] Example 4 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 80mL of ultrapure water into a beaker and place the beaker in a 55℃ constant temperature water bath. Turn on the digital display magnetic stirrer and adjust the speed to 350r / min. Slowly add 3.0g of silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 6.0g of carboxymethyl chitosan and 5.0g of purified N-isopropylacrylamide-hydroxyethyl methacrylate copolymer (NIPAM-HEMA copolymer) monomer in sequence. Maintain a water bath temperature of 55°C and continue stirring at 250r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-Isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) were dissolved in 100 ml of deionized water at a molar ratio of 1:1.2 to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 28 min to thoroughly remove dissolved oxygen and prevent it from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator. The polymerization reaction was carried out at 50 °C for 5 h. After the polymerization reaction was completed, the reaction system was quickly cooled in an ice-water bath at 5 °C. The polymerization reaction was terminated to obtain a NIPAM-HEMA copolymer containing impurities. This NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, followed by dialyzed with deionized water for 50 hours to remove small monomer molecules and initiator fragments. After dialysis, the purified NIPAM-HEMA copolymer was obtained. The reaction mixture contained 8% N-isopropylacrylamide (NIPAM) and 92% hydroxyethyl methacrylate (HEMA) by mass, and the total mass percentage of the above components was 100%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 7:100. The dialysis bag used in the dialysis has a molecular weight cutoff of MWCO: 8000 Da; Step 1.3: Add 1.6g of sodium hyaluronate and 0.015g of phenoxyethanol to mixed solution A, adjust the stirring speed to 100r / min, and continue stirring for 50min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.04g of graphene oxide (GO) to the basic mixed solution, turn on a high-power ultrasonic disperser with a power of 300W, and ultrasonically disperse for 45min while maintaining magnetic stirring at 500r / min to ensure that the GO sheets are uniformly dispersed in the solution and avoid agglomeration, thus obtaining mixed solution B. Step 2.2: Add 1.2 g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.03 g of N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 500 rpm for 35 min until completely dissolved. Then add 0.08 g of ammonium persulfate (APS) initiator and stir for 30 min. Slowly add 0.7 g of lanthanum chloride (LaCl3) while maintaining the stirring speed for 30 min, so that La... 3+The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.05 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 30 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links with ionic and covalent cross-linking to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The crosslinking precursor solution C was slowly poured into a silicone rubber mold. The filled mold was placed in an 80°C constant temperature water bath and the polymerization reaction was carried out at a constant temperature for 5 hours to allow NIPAM-HEMA to fully polymerize, PEGDA to complete covalent crosslinking, and the ionic crosslinking network and dynamic Schiff base bond crosslinking network to be further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle, ensuring uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and the surface was rinsed 5 times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was placed in a 37°C, 65% humidity constant temperature and humidity chamber for 36 hours to further stabilize the crosslinking network, resulting in a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0026] Example 5 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 80mL of ultrapure water into a beaker and place the beaker in a 55℃ constant temperature water bath. Turn on the digital display magnetic stirrer and adjust the speed to 350r / min. Slowly add 3.0g of silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 5.0g of carboxymethyl chitosan and 3.5g of purified N-isopropylacrylamide-hydroxyethyl methacrylate copolymer (NIPAM-HEMA copolymer) monomer in sequence. Maintain a water bath temperature of 55°C and continue stirring at 100r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) in a molar ratio of 1:1.5 were thoroughly dissolved in 100 ml of deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 30 min to thoroughly remove dissolved oxygen and prevent it from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator, and the polymerization reaction was carried out at 40 °C for 7 h. After the polymerization reaction was completed, the reaction system was quickly placed in an ice-water bath at 4 °C to cool and terminate the polymerization. The reaction yielded a NIPAM-HEMA copolymer containing impurities. This NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, followed by dialyzed with deionized water for 72 hours to remove small molecule monomers and initiator fragments. After dialysis, the purified NIPAM-HEMA copolymer was obtained. The reaction mixture contained 12% N-isopropylacrylamide (NIPAM) and 88% hydroxyethyl methacrylate (HEMA) by mass, and the total mass percentage of the above components was 100%. The ratio of the amount of azobisisobutyronitrile (AIBN) to the total amount of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 10:100. The dialysis bag used in the dialysis has a molecular weight cutoff of MWCO: 10000 Da; Step 1.3: Add 1.6g of sodium hyaluronate and 0.02g of phenoxyethanol to mixed solution A, set the stirring speed to 250r / min, and continue stirring for 50min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.04g of graphene oxide (GO) to the basic mixed solution, turn on a 250W high-power ultrasonic disperser, ultrasonically disperse for 45min, and simultaneously maintain magnetic stirring at 500r / min to ensure that the GO sheets are uniformly dispersed in the solution and avoid agglomeration, thus obtaining mixed solution B. Step 2.2: Add 1.2 g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.03 g of N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 500 rpm for 35 min until completely dissolved. Then add 0.08 g of ammonium persulfate (APS) initiator, stir for 30 min, and slowly add 0.8 g of lanthanum chloride (LaCl3), maintaining the stirring speed, and stir for 25 min to allow the La... 3+The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.05 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 20 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links with ionic and covalent cross-linking to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The crosslinking precursor solution C was slowly poured into a silicone rubber mold. The filled mold was placed in a 65°C constant temperature water bath and the polymerization reaction was carried out at a constant temperature for 4 hours to allow NIPAM-HEMA to fully polymerize, PEGDA to complete covalent crosslinking, and the ionic crosslinking network and dynamic Schiff base bond crosslinking network to be further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle and ensures uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and the surface was rinsed 5 times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was placed in a 37°C, 75% humidity constant temperature and humidity chamber for 36 hours to further stabilize the crosslinking network, resulting in a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0027] Example 6 Step 1: Prepare the basic mixed solution; The specific process is as follows: Step 1.1: Pour 80mL of ultrapure water into a beaker and place the beaker in a 50℃ constant temperature water bath. Turn on the digital display magnetic stirrer and adjust the speed to 300r / min. Slowly add 3.0g of silk fibroin and continue stirring until the silk fibroin is completely dissolved and a transparent and uniform silk fibroin solution is formed. Step 1.2: In the silk fibroin solution, add 5.0g of carboxymethyl chitosan and 3.5g of purified N-isopropylacrylamide-hydroxyethyl methacrylate copolymer (NIPAM-HEMA copolymer) monomer in sequence. Maintain a water bath temperature of 50°C and continue stirring at 200r / min until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. The method for preparing the purified NIPAM-HEMA copolymer is as follows: N-Isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) in a 1:1 molar ratio were thoroughly dissolved in 100 ml of deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 30 min to remove dissolved oxygen and prevent it from inhibiting the polymerization reaction. Azobisisobutyronitrile (AIBN) was then added to the reaction mixture as a free radical initiator, and the polymerization reaction was carried out at 60 °C for 6 h. After the polymerization reaction was completed, the reaction system was rapidly cooled in an ice-water bath at 4 °C to terminate the polymerization. The polymerization reaction yielded a NIPAM-HEMA copolymer containing impurities. This impurity-containing NIPAM-HEMA copolymer was dialyzed against methanol for 24 hours, followed by dialyzed against deionized water for 60 hours to remove small monomer molecules and initiator fragments. After dialysis, the purified NIPAM-HEMA copolymer was obtained. The reaction mixture contained 15% N-isopropylacrylamide (NIPAM) and 85% hydroxyethyl methacrylate (HEMA) by mass, and the total mass percentage of the above components was 100%. The ratio of the amount of azobisisobutyronitrile (AIBN) to the total amount of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 10:100. The dialysis bag used in the dialysis had a molecular weight cutoff of MWCO: 14000 Da; Step 1.3: Add 1.6g of sodium hyaluronate and 0.02g of phenoxyethanol to mixed solution A, set the stirring speed to 200r / min, and continue stirring for 40min to ensure that the moisturizing components and preservatives are evenly dispersed to obtain the basic mixed solution; Step 2: Prepare a mixed crosslinking solution using a basic mixed solution; The specific process is as follows: Step 2.1: Add 0.04g of graphene oxide (GO) to the basic mixed solution, turn on a 200W high-power ultrasonic disperser, ultrasonically disperse for 40min, and simultaneously maintain magnetic stirring at 400r / min to ensure that the GO sheets are uniformly dispersed in the solution and avoid agglomeration, thus obtaining mixed solution B. Step 2.2: Add 1.2 g of polyethylene glycol diacrylate (PEGDA) (molecular weight 600) and 0.03 g of N,N-methylenebisacrylamide (MBA) to mixed solution B, and stir at 400 r / min for 30 min until completely dissolved. Then add 0.08 g of ammonium persulfate (APS) initiator, stir for 25 min, and slowly add 0.8 g of lanthanum chloride (LaCl3), maintaining the stirring speed, and stir for 30 min to allow the La... 3+The carboxyl groups of carboxymethyl chitosan are fully combined to form a stable and reversible ionic cross-linking network, which simulates the preliminary skeletal structure of muscle fibers. Then, 0.05 g of o-phthalaldehyde (OPA) is slowly added dropwise and stirred for 25 min to allow OPA to form a dynamic Schiff base bond cross-linking network with the amino groups of silk fibroin, which synergistically cross-links ionicly and covalently to obtain a mixed cross-linking solution. Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions; The crosslinking precursor solution C was slowly poured into a silicone rubber mold. The filled mold was placed in a 70°C constant temperature water bath and the polymerization reaction was carried out at a constant temperature for 3 hours to allow NIPAM-HEMA to fully polymerize, PEGDA to complete covalent crosslinking, and the ionic crosslinking network and dynamic Schiff base bond crosslinking network to be further stabilized, forming a complete three-dimensional network structure that accurately simulates the fiber network of skeletal muscle and ensures uniform mechanical properties of the hydrogel. After the polymerization reaction was completed, the mold was removed and allowed to cool naturally to room temperature. After cooling, the hydrogel was slowly removed from the mold and the surface was rinsed 5 times with ultrapure water to thoroughly remove any unreacted residual reagents. The rinsed hydrogel was placed in a 25°C, 70% humidity constant temperature and humidity chamber for 36 hours to further stabilize the crosslinking network, resulting in a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

[0028] The compressive strength of the stiffened ankle anti-torsion hydrogel patch was measured at loading speeds of 0.2 mm / min and 2 mm / min to simulate the strength change of the hydrogel under instantaneous impact during application. The results are as follows: Figure 1 As shown, the compressive strength is 0.34 MPa at a loading speed of 0.2 mm / min and 1.2 MPa at a loading speed of 2 mm / min. This indicates that the compressive strength of the water-based kinetic adaptive stiffening ankle anti-torsion hydrogel patch varies significantly under different loading speeds. This demonstrates that the water-based kinetic adaptive stiffening ankle anti-torsion hydrogel patch can form a rigid protective support under instantaneous impact, effectively limiting excessive ankle twisting.

Claims

1. A method for preparing a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, characterized in that, The specific steps are as follows: Step 1: Prepare the basic mixed solution; Step 2: Prepare a mixed crosslinking solution from a basic mixed solution; Step 3: Prepare a myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch by mixing cross-linking solutions.

2. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 1, characterized in that, The specific process of step 1 is as follows: Step 1.1: Pour ultrapure water into a beaker and place the beaker in a constant temperature water bath. Turn on the digital display magnetic stirrer, slowly add silk fibroin and stir continuously until the silk fibroin is completely dissolved to form a transparent and uniform silk fibroin solution. Step 1.2: In the silk fibroin solution, carboxymethyl chitosan and purified NIPAM-HEMA copolymer are added sequentially. The water bath temperature is maintained and stirring is continued until all solid components are completely dissolved to form a homogeneous and transparent mixed solution A. Step 1.3: Add sodium hyaluronate and phenoxyethanol to mixed solution A, and continue stirring to ensure uniform dispersion, thus obtaining the basic mixed solution.

3. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 2, characterized in that, In steps 1.1 to 1.3, the mass ratio of ultrapure water, silk fibroin, carboxymethyl chitosan, purified NIPAM-HEMA copolymer, sodium hyaluronate, and phenoxyethanol is 3988~7976:150~250:250~450:175~350:80~120:

1.

4. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 2, characterized in that, In step 1.1, the temperature of the constant temperature water bath is 45℃~55℃, and the stirring speed is 200r / min~350r / min; In step 1.2, the stirring speed is 100 r / min to 250 r / min; In step 1.3, the stirring speed is 100 r / min to 250 r / min, and the stirring time is 25 min to 50 min.

5. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 2, characterized in that, In step 1.2, the method for preparing the purified NIPAM-HEMA copolymer is as follows: N-isopropylacrylamide and hydroxyethyl methacrylate in a molar ratio of 1:1 to 1.5 were fully dissolved in deionized water to obtain a reaction mixture. Nitrogen gas was then continuously bubbled into the reaction mixture for 25 to 30 minutes. Azobisisobutyronitrile was then added to the reaction mixture, and polymerization was carried out at 25°C to 60°C for 4 to 8 hours. After the polymerization was completed, the reaction system was quickly placed in an ice-water bath at 4°C to 8°C to terminate the polymerization and obtain NIPAM-HEMA copolymer containing impurities. The obtained NIPAM-HEMA copolymer containing impurities was dialyzed with methanol for 24 hours, and then dialyzed with deionized water for 48 to 72 hours. After the dialyz was completed, the purified NIPAM-HEMA copolymer was obtained. In the reaction mixture, the sum of the mass fractions of N-isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) is 5%~15%, the mass fraction of deionized water is 85%~95%, and the sum of the mass percentages of the above components is 100%. The molar ratio of azobisisobutyronitrile (AIBN) to the total molar ratio of N-isopropylacrylamide (NIPAM) to hydroxyethyl methacrylate (HEMA) is 5~15:

100.

6. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 2, characterized in that, The specific process of step 2 is as follows: Step 2.1: Add graphene oxide to the basic mixed solution, turn on the ultrasonic disperser for ultrasonic dispersion, and stir magnetically at the same time to obtain mixed solution B; Step 2.2: Add polyethylene glycol diacrylate and N,N-methylenebisacrylamide to mixed solution B, stir until completely dissolved, then add ammonium persulfate initiator and stir, then slowly add lanthanum chloride and stir, then slowly add phthalaldehyde and stir to obtain a mixed crosslinking solution.

7. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 6, characterized in that, In steps 2.1 to 2.2, the mass ratio of graphene oxide, polyethylene glycol diacrylate, N,N-methylenebisacrylamide, ammonium persulfate, lanthanum chloride, and phthalaldehyde is 1:26~90:0.6~2:1.6~5:16~40:1~3. The mass ratio of graphene oxide to phenoxyethanol is 1:0.375~1.

8. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 1, characterized in that, The specific process of step 3 is as follows: slowly pour the mixed crosslinking solution into the silicone rubber mold, place the filled silicone rubber mold into a constant temperature water bath for constant temperature polymerization reaction, after the polymerization reaction is completed, remove the silicone rubber mold and let it cool naturally to room temperature, after cooling, a semi-finished hydrogel is obtained, slowly remove the semi-finished hydrogel from the silicone rubber mold, rinse the surface with ultrapure water to completely remove the unreacted residual reagents on the surface, place the rinsed semi-finished hydrogel in a constant temperature and humidity chamber for curing, and obtain a myogenic mechanical adaptive stiffening ankle anti-torsion hydrogel patch.

9. The method for preparing the myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch according to claim 8, characterized in that, The isothermal polymerization reaction temperature is 65℃~80℃, the isothermal polymerization reaction time is 2.5h~5h, the curing temperature is 25℃~37℃, the curing humidity is 65%~75%, and the curing time is 24h~36h.

10. A myogenic biomechanical adaptive stiffening ankle anti-torsion hydrogel patch, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 9.

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