A preparation process and application of a medical material for highly coagulated water

Abstract

The present invention relates to a preparation process and application of a medical material for highly condensed water. By subjecting sodium hyaluronate to silanization modification, the sodium hyaluronate has higher purity and moisturizing performance. Then, the starch is subjected to porous treatment to increase the specific surface area of the starch, so that there are more binding sites. After the starch is subjected to amino modification, the amino functional group can form a stronger bond with functional groups such as hydrogen bonds. In addition, carboxymethyl cellulose and acrylamide-based gel solutions are prepared. The porous amino starch / silanized sodium hyaluronate composite material and carboxymethyl cellulose are added to the gel solution, and after heating and shaping, a medical dressing with excellent mechanical properties, strong moisturizing property and good antibacterial and anti-inflammatory effects can be obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of medical materials, and mainly relates to a preparation process and application of a medical material with high coagulation water, and particularly relates to a preparation process of a high coagulation water medical dressing. Background Art

[0002] Hydrogel dressings have the advantages of good air permeability, high moisture retention, excellent mechanical properties, and low sensitivity, and have broad application potential in wound healing. Therefore, many scholars have studied hydrogel dressings. For example, in order to improve the protection ability and antibacterial properties of the dressing, a biodegradable antibacterial medical hydrogel dressing was studied; in order to improve the moisture retention performance of the hydrogel dressing, various moisture retention components were added during the preparation process, and the gel had good mechanical properties by adding substances such as glycerol.

[0003] Hyaluronic acid (HA) has been widely used in the fields of medical beauty and medical materials. Because it has important physiological functions such as maintaining the extracellular space, regulating osmotic pressure, and lubrication, it can play an important biological function in wound healing, thereby reducing the inflammatory response. In addition, it also has the characteristics of improving cell invasiveness, scavenging free radicals, and antioxidant properties.

[0004] Although HA has excellent properties such as good biocompatibility, high hydrophilicity, and good adhesion, the mechanical properties and moisture retention of the prepared hydrogel are still limited. In addition, the antibacterial and anti-inflammatory properties also need to be further improved. The structure of hyaluronic acid contains chemical active sites such as hydroxyl groups and carboxyl groups, and can be subjected to various chemical modifications to endow it with specific functions. It has been reported that hyaluronic acid derivatives include acetylated hyaluronic acid, quaternized hyaluronic acid, carboxymethylated hyaluronic acid, silanized hyaluronic acid, etc. There is a literature report that silanized hyaluronic acid has better moisture retention performance, no cytotoxicity, no skin irritation, and can promote the proliferation of keratinocytes, and can be used to prepare cosmetics and medical accessories with skin moisturizing and repair functions. However, there are few reports on the preparation method of silanized hyaluronic acid.

[0005] Therefore, in this paper, sodium hyaluronate was silanized and modified, and a variety of antibacterial components and water-locking structures were added to the dressing, thereby preparing a medical material with high coagulation water. Summary of the Invention

[0006] The present invention relates to a preparation process and application of a medical material for highly condensed water. First, sodium hyaluronate is subjected to silanization modification, and then starch is subjected to porous treatment to increase the specific surface area of the starch, so that there are more binding sites. After the starch is subjected to amino modification, the amino functional group can form a stronger bond with functional groups such as hydrogen bonds. In addition, carboxymethyl cellulose and acrylamide-based gel solution are prepared. The porous amino starch / silanized sodium hyaluronate composite material and carboxymethyl cellulose are added to the gel solution, and after heating and molding, a medical dressing with excellent mechanical properties, strong moisturizing property and good antibacterial and anti-inflammatory effects can be obtained. The specific synthesis steps are as follows:

[0007] S1. Preparation of modified sodium hyaluronate: Take 1-3 g of sodium hyaluronate and dissolve it in 10-50 ml of N,N-dimethylformamide. Slowly add 0.1-1 g of 1,1-dimethoxy-silane-1-acetate, then dropwise add 10-50 μl of hydrochloric acid with a mass fraction of 25-35 wt%, and then add 5-10 mg of HMCM-22 molecular sieve. Stir at 30-50 °C for 5-16 h. After the reaction is completed, pour 100-500 ml of absolute ethanol into the reaction solution. After the solution settles, wash and dry the substrate to obtain silanized sodium hyaluronate; in this step, hydrochloric acid and molecular sieve are used as catalysts for the reaction. During the reaction, both of them can provide protons, which efficiently promotes the progress of the reaction, and two different types of catalysts also play a synergistic role; this preparation method has controllable conditions and is green and environmentally friendly; the silanized sodium hyaluronate prepared in this step has the advantages of high purity, no irritation to the skin and high moisturizing performance;

[0008] S2. Preparation of porous amino starch: Weigh 10-20 g of corn starch and place it in a three-necked flask. Add 30-40 mL of a 10% hydrochloric acid solution. Heat and stir the obtained starch emulsion at 50-60 °C for 3-5 h, and then use 1M Na 2 CO 3The solution is neutralized with hydrochloric acid. When the pH is neutral, stirring is continued for 15 - 30 min, and it is washed 3 - 5 times with deionized water to remove other impurities in the solution. The product after suction filtration is placed in a drying oven at 50 °C to obtain porous starch mpSt. 13 - 15 g of porous starch is dissolved in 15 - 20 mL of epichlorohydrin containing 0.3 - 0.8 mL of concentrated HCl. The mixture is stirred at 90 - 110 °C for 16 - 24 h and then washed 3 - 5 times with absolute ethanol, and vacuum dried at 60 °C for later use. 6 - 9 g of halogenated starch is dissolved in 50 mL of 0.1 M sodium hydroxide, and then 10 - 15 g of ethylenediamine is added and reacted at 60 °C for 24 h. After the reaction, it is continued to be washed 3 - 5 times with absolute ethanol and vacuum dried at 60 °C. Then it is ball-milled with a ball mill to obtain porous amino starch with a smaller particle size. In this step, the starch is subjected to porous treatment, which is beneficial to increasing its specific surface area. The porous structure is also beneficial to the attachment of other functional groups, thereby increasing the number of functional groups in the starch. The amino functional group and other functional groups can form network structures such as hydrogen bonds, which can play a water-locking effect. In addition, it can also provide a certain antibacterial effect. The ball-milling treatment makes the prepared material have a smaller size and can be better dispersed in other substances.

[0009] S3. Preparation of porous amino starch / silylated sodium hyaluronate composite material: Take 0.5 - 2.5 g of the silylated sodium hyaluronate obtained in step S1 and 2.5 - 5 g of the porous amino starch obtained in step S2 and place them in a beaker. Then add 30 - 50 ml of deionized water, and use the ultrasonic-microwave method to mix them evenly. The ultrasonic conditions are 160 w and 5 min. In this step, after mixing the two, the composite material has high water retention, and the operation is simple, improving the dispersion effect of the two. Both starch and sodium hyaluronate contain amino and hydroxyl functional groups, and intermolecular forces can be generated between the two substances, so they are dispersed more evenly and have a higher water content.

[0010] S4. Preparation of carboxymethyl cellulose: The waste straw is placed in a crusher for crushing. 20 - 30 g of the crushed straw is placed in a three-necked flask, 5 - 8 g of sodium hydroxide and 60 - 80 ml of ethanol are poured into the three-necked flask, and it is stirred at 40 °C for 3 - 5 h. Then 20 - 30 ml of chloroacetic acid is added, and it is stirred at 60 - 80 °C for 2.5 - 4.5 h. Then glacial acetic acid is added for neutralization, and stirring is continued for 0.3 - 0.5 h. Then it is filtered and washed with ethanol, and dried to obtain carboxymethyl cellulose. The carboxymethyl cellulose prepared in this step contains a large number of hydrophilic groups, so it has a high water content. In addition, using waste straw as a raw material realizes the secondary utilization of resources, which is beneficial to environmental protection. The raw materials are cheap and easy to obtain, and the economic cost is also reduced.

[0011] S5. Preparation of acrylamide-based hydrogel solution: Take 3.05 - 3.85 g of acrylamide (AM), 0.015 - 0.025 g of N,N'-methylenebisacrylamide (MBA), and 0.02 - 0.03 g of ammonium persulfate (APS) and place them in a beaker. Then add 1 - 3 ml of glycerol, 7 - 14 ml of PBS buffer, 0.6 - 1.3 g of curcumin, and 0.2 - 0.8 g of cinnamon essential oil and stir for 15 - 30 min to obtain the acrylamide-based hydrogel solution. A highly cross-linked network structure can be formed inside the acrylamide-based hydrogel solution prepared in this step, which is beneficial to improving the mechanical effect of the gel. The addition of glycerol can improve the moisture retention characteristics of the material, and the use of PBS buffer can provide more ions for the gel solution, enhancing the comprehensive performance of the gel. In addition, the addition of curcumin and cinnamon essential oil endows the material with anti-inflammatory and antibacterial properties, and since the two are different types of antibacterial components, the antibacterial effect is better improved after compounding. It should be noted that this network structure with multiple cross-linking points can well fix curcumin and make it play a more stable effect.

[0012] S6. Preparation of high-coagulable water composite hydrogel: Take 1.3 - 2.6 g of the composite material prepared in step S3 and 1 - 2 g of carboxymethyl cellulose prepared in step S4 and add them to the acrylamide-based hydrogel solution prepared in step S5. After stirring for 10 - 30 min, pour it into a PTFE mold and place it in an oven at 50 °C to obtain a high-coagulable water composite hydrogel with a highly cross-linked network. The high-coagulable water composite hydrogel prepared in step S6 has a highly cross-linked network structure because a large number of hydroxyl and amino functional groups are contained in the materials used, and hydrogen bonds can be formed between them, while sodium ions, etc. can serve as cross-linking points. Therefore, the gel not only has a highly cross-linked network structure inside but also shows high mechanical properties and good moisture retention characteristics. In addition, due to the rich amino functional groups and curcumin components in the gel structure, it also has a certain antibacterial effect and can be used as a medical dressing.

[0013] Preferably: In step S1, take 2.68 g of sodium hyaluronate and dissolve it in 35 ml of N,N-dimethylformamide.

[0014] Preferably: In step S1, add 0.53 g of 1,1-dimethoxy-silane-1-acetate, 25 μl of hydrochloric acid, and 10 mg of HMCM-22 molecular sieve, and stir at 50 °C for 12 h.

[0015] Preferably: In step S2, weigh 15 g of corn starch, add 30 mL of 10% hydrochloric acid solution, heat and stir at 60 °C for 5 h. After the pH is neutral, continue to stir for 20 min.

[0016] Preferably: In step S2, 10 g of porous starch is dissolved in 20 mL of epichlorohydrin containing 0.6 mL of concentrated HCl, and the mixture is stirred at 110 °C for 16 h; 6 g of halogenated starch is dissolved in 50 mL of 0.1 M sodium hydroxide, and then 10 g of ethylenediamine is added and reacted at 60 °C for 24 h.

[0017] Preferably: In step S3, 2.13 g of the silylated sodium hyaluronate obtained in step S1 and 3.87 g of the porous amino starch obtained in step S2 are placed in a beaker, and then 50 ml of deionized water is added.

[0018] Preferably: In step S4, 20 g of crushed straw, 5.6 g of sodium hydroxide and 80 ml of ethanol are added, stirred at 40 °C for 5 h, then 20 ml of chloroacetic acid is added, stirred at 65 °C for 4 h, and after neutralization, stirring is continued for 0.4 h.

[0019] Preferably: In step S5, 3.65 g of acrylamide AM, 0.023 g of N,N - methylenebisacrylamide MBA and 0.027 g of ammonium persulfate APS are placed in a beaker, then 2 ml of glycerol, 13 ml of PBS buffer solution, 0.75 g of curcumin and 0.3 g of cinnamon essential oil are added, and stirred for 30 min.

[0020] Preferably: In step S6, 2.5 g of the composite material prepared in step S3 and 2 g of the carboxymethyl cellulose prepared in step S4 are added to the acrylamide - based hydrogel solution prepared in step S5, and stirred for 30 min.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1. In the present invention, hydrochloric acid and molecular sieve are used as reaction catalysts. During the reaction, both of them can provide protons, which efficiently promotes the progress of the reaction, and the two different types of catalysts also play a synergistic role; the preparation method has controllable conditions and is green and environmentally friendly; the prepared silylated sodium hyaluronate has the advantages of high purity, no irritation to the skin and high moisturizing performance.

[0023] 2. The present invention performs porous treatment on starch, which is beneficial to increasing its specific surface area, and the porous structure is also beneficial to the attachment of other functional groups, thus increasing the number of functional functional groups in starch; the amino functional group and other functional groups can form network structures such as hydrogen bonds, which can play a water - locking effect and can also provide a certain antibacterial effect; the ball - milling treatment makes the prepared material have a smaller size and can be better dispersed in other substances.

[0024] 3. The present invention performs ultrasonic-microwave treatment on porous amino starch and silylated sodium hyaluronate. After mixing the two, the composite material has high water retention, simple operation, and improved dispersion effect; both starch and sodium hyaluronate have amino and hydroxyl functional groups, and intermolecular forces can be generated between the two substances, so they are more evenly dispersed and have higher water content.

[0025] 4. The carboxymethyl cellulose prepared by the present invention contains a large number of hydrophilic groups, so it has a high water content. In addition, using waste straw as a raw material realizes the secondary utilization of resources, which is beneficial to environmental protection. The raw materials are cheap and easy to obtain, and the economic cost is also reduced.

[0026] 5. A highly cross-linked network structure can be formed inside the acrylamide-based hydrogel solution prepared by the present invention, which is beneficial to improving the mechanical effect of the gel. The addition of glycerol can improve the moisturizing property of the material, and the use of PBS buffer solution can provide more ions for the gel solution, so that the comprehensive performance of the gel is improved; the addition of curcumin and cinnamomum essential oil endows the material with antibacterial properties, and because the two are different types of antibacterial components, the antibacterial effect is better improved after compounding. In addition, this compounding addition method also endows the material with a significant anti-inflammatory effect; it should be noted that this multi-crosslinking point network structure can well fix curcumin and make it play a more stable effect.

[0027] 6. The highly coagulated water composite hydrogel prepared by the present invention has a highly cross-linked network structure because a large number of hydroxyl and amino functional groups are contained in the materials used, and hydrogen bonds can be formed between them, and sodium ions, etc. can be used as cross-linking points. Therefore, the gel not only has a highly cross-linked network structure inside but also shows high mechanical properties and good moisturizing properties, and it is also found that the gel has a certain repair effect. In addition, due to the rich amino functional groups and curcumin components in the gel structure, it also has a certain antibacterial effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0029] Figure 1 It is the moisturizing property diagram of the gel materials prepared in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention.

[0030] Figure 2 It is the microscopic morphology diagram of starch in Comparative Example 3 of the present invention.

[0031] Figure 3 It is the microscopic morphology diagram of starch in Comparative Example 4 of the present invention.

[0032] Figure 4 It is the swelling data diagram of the gel materials prepared in Example 3 and Comparative Example 5 of the present invention.

[0033] Figure 5 It is the antibacterial data diagram of the gel materials prepared in Example 4, Comparative Example 6 and Comparative Example 7 of the present invention. Detailed implementation manners

[0034] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the content of the present invention and are not used to limit the present invention.

[0035] Example 1:

[0036] S1. Preparation of modified sodium hyaluronate: Take 2.68 g of sodium hyaluronate and dissolve it in 35 ml of N,N-dimethylformamide. Slowly add 0.53 g of 1,1-dimethoxy-silane-1-acetate, then dropwise add 25 ul of hydrochloric acid with a mass fraction of 25-35 wt%, and then add 10 mg of HMCM-22 molecular sieve. Stir at 50 °C for 12 h. After the reaction is completed, pour 100-500 ml of absolute ethanol into the reaction solution. After the solution settles, wash and dry the substrate to obtain silylated sodium hyaluronate;

[0037] S2. Preparation of porous amino starch: Weigh 15 g of corn starch and place it in a three-necked flask. Add 30 mL of a 10% hydrochloric acid solution. Heat and stir the obtained starch emulsion at 60 °C for 5 h, and then use 1 M Na 2 CO 3 solution to neutralize the hydrochloric acid. When the pH is neutral, continue to stir for 20 min, wash with deionized water 3-5 times to remove other impurities in the solution. Place the filtered product in a drying oven at 50 °C to dry to obtain porous starch mpSt; Dissolve 10 g of porous starch in 20 mL of epichlorohydrin containing 0.6 ml of concentrated HCl. Stir the mixture at 110 °C for 16 h, then wash with absolute ethanol 3-5 times, and dry in vacuum at 60 °C for use; Dissolve 6 g of halogenated starch in 50 mL of 0.1 M sodium hydroxide, then add 10 g of ethylenediamine and react at 60 °C for 24 h. After the reaction is completed, continue to wash with absolute ethanol 3-5 times, dry in vacuum at 60 °C, and then perform ball milling treatment with a ball mill to obtain porous amino starch with a smaller particle size;

[0038] S3. Preparation of porous amino starch / silylated sodium hyaluronate composite material: Take 2.13 g of the silylated sodium hyaluronate obtained in step S1 and 3.87 g of the porous amino starch obtained in step S2 and place them in a beaker. Then add 50 ml of deionized water and use the ultrasonic-microwave method to mix them evenly. The ultrasonic conditions are 160 w and 5 min;

[0039] S4. Preparation of carboxymethyl cellulose: Place the waste straw in a crusher for crushing. Put 20 g of the crushed straw into a three-necked flask, pour 5.6 g of sodium hydroxide and 80 ml of ethanol into the three-necked flask, stir at 40 °C for 5 h, then add 20 ml of chloroacetic acid, stir at 65 °C for 4 h, add glacial acetic acid for neutralization, continue to stir for 0.4 h, and then filter and wash with ethanol. After drying, carboxymethyl cellulose is obtained;

[0040] S5. Preparation of acrylamide-based hydrogel solution: Take 3.65 g of acrylamide AM, 0.023 g of N,N'-methylenebisacrylamide MBA, and 0.027 g of ammonium persulfate APS and place them in a beaker. Then add 2 ml of glycerol, 13 ml of PBS buffer solution, 0.75 g of curcumin, and 0.3 g of cinnamon essential oil and stir for 30 min to obtain the acrylamide-based hydrogel solution;

[0041] S6. Preparation of highly coagulated water composite hydrogel: Take 2.5 g of the composite material prepared in step S3 and 2 g of the carboxymethyl cellulose prepared in step S4 and add them to the acrylamide-based hydrogel solution prepared in step S5. After stirring for 30 min, pour it into a PTFE mold and place it in an oven at 50 °C to obtain a highly coagulated water composite hydrogel with a high cross-linked network; this hydrogel has a certain antibacterial effect and can be used as a medical dressing.

[0042] Comparative example 1: Except that hydrochloric acid is not added in step S1, the other steps are the same as those in Example 1.

[0043] Comparative example 2: Except that HMCM-22 molecular sieve is not added in step S1, the other steps are the same as those in Example 1.

[0044] Figure 1 This is the moisture retention graph of the gel materials prepared in Example 1, Comparative example 1, and Comparative example 2 of the present invention. From Figure 1 It can be seen that: Example 1 has more persistent moisture retention characteristics. This is because the degree of silylation modification of the sodium hyaluronate used in Example 1 is higher, and there are many characteristic functional groups in the molecular structure. Therefore, the modified sodium hyaluronate has the characteristics of higher purity and stronger moisture retention effect.

[0045] Example 2:

[0046] S1. Preparation of modified sodium hyaluronate: Dissolve 1.69 g of sodium hyaluronate in 30 ml of N,N-dimethylformamide. Slowly add 0.31 g of 1,1-dimethoxy-silane-1-acetate, then dropwise add 10 μl of hydrochloric acid with a mass fraction of 25-35 wt%. Then add 5 mg of HMCM-22 molecular sieve and stir at 50 °C for 10 h. After the reaction, pour 100-500 ml of absolute ethanol into the reaction solution. After the solution settles, wash and dry the substrate to obtain silylated sodium hyaluronate;

[0047] S2. Preparation of porous amino starch: Weigh 15 g of corn starch and place it in a three-necked flask. Add 30 mL of 10% hydrochloric acid solution. Heat and stir the resulting starch emulsion at 60 °C for 3 h. Then use 1 M Na 2 CO 3 solution to neutralize the hydrochloric acid. When the pH is neutral, continue stirring for 30 min, wash with deionized water 3-5 times to remove other impurities in the solution. Place the filtered product in a drying oven at 50 °C to dry to obtain porous starch mpSt. Dissolve 10 g of porous starch in 15 mL of epichlorohydrin containing 0.5 ml of concentrated HCl. Stir the mixture at 90 °C for 24 h, then wash with absolute ethanol 3-5 times and dry in vacuo at 60 °C for use. Dissolve 8.2 g of halogenated starch in 50 mL of 0.1 M sodium hydroxide, then add 10.8 g of ethylenediamine and react at 60 °C for 24 h. After the reaction, continue to wash with absolute ethanol 3-5 times and dry in vacuo at 60 °C. Then perform ball milling treatment with a ball mill to obtain porous amino starch with a smaller particle size;

[0048] S3. Preparation of porous amino starch / silylated sodium hyaluronate composite: Take 1.32 g of the silylated sodium hyaluronate obtained in step S1 and 4.68 g of the porous amino starch obtained in step S2 and place them in a beaker. Then add 30 ml of deionized water and use the ultrasonic-microwave method to mix them evenly. The ultrasonic conditions are 160 w and 5 min;

[0049] S4. Preparation of carboxymethyl cellulose: Place the waste straw in a crusher for crushing. Put 20 g of the crushed straw into a three-necked flask, pour 5 g of sodium hydroxide and 60 ml of ethanol into the three-necked flask. Stir at 40 °C for 3 h, then add 20 ml of chloroacetic acid and stir at 60 °C for 2.5 h. Then add glacial acetic acid for neutralization, continue stirring for 0.3 h, and then filter and wash with ethanol. After drying, carboxymethyl cellulose is obtained;

[0050] S5. Preparation of acrylamide-based hydrogel solution: Take 3.05 g of acrylamide (AM), 0.015 g of N,N'-methylenebisacrylamide (MBA), and 0.02 g of ammonium persulfate (APS) and place them in a beaker. Then add 3 ml of glycerol, 12 ml of PBS buffer solution, 0.6 g of curcumin, and 0.2 g of cinnamon essential oil, and stir for 30 min to obtain the acrylamide-based hydrogel solution;

[0051] S6. Preparation of high-coagulation water composite hydrogel: Take 1.3 g of the composite material prepared in step S3 and 1 g of carboxymethyl cellulose prepared in step S4 and add them to the acrylamide-based hydrogel solution prepared in step S5. After stirring for 30 min, pour it into a PTFE mold and place it in an oven at 50 °C to obtain a high-coagulation water composite hydrogel with a high cross-linked network; This hydrogel has a certain antibacterial effect and can be used as a medical dressing.

[0052] Comparative Example 3: Except that the starch is not subjected to porous treatment in step S2, the other steps are the same as those in Example 2.

[0053] Comparative Example 4: Except that the porous starch is not subjected to amino modification in step S2, the other steps are the same as those in Example 2.

[0054] Figure 2 This is the microscopic morphology diagram of the starch prepared in Comparative Example 3 of the present invention. Figure 3 This is the microscopic morphology diagram of the starch prepared in Comparative Example 4 of the present invention. It can be seen from Figure 2 that the surface of the starch is smooth. It can be seen from Figure 3 that the surface of the starch is damaged and presents a porous structure. The porous structure increases the specific surface area of the starch, provides more sites, is conducive to the combination with amino groups, and thus improves the comprehensive performance of the composite material.

[0055] Example 3:

[0056] S1. Preparation of modified sodium hyaluronate: Take 2.96 g of sodium hyaluronate and dissolve it in 30 ml of N,N-dimethylformamide. Slowly add 0.14 g of 1,1-dimethoxy-silane-1-acetate, then dropwise add 30 μl of hydrochloric acid with a mass fraction of 25-35 wt%, and then add 7 mg of HMCM-22 molecular sieve. Stir at 50 °C for 14 h. After the reaction is completed, pour 100-500 ml of absolute ethanol into the reaction solution. After the solution settles, wash and dry the substrate to obtain silylated sodium hyaluronate;

[0057] S2. Preparation of porous amino starch: Weigh 18.6 g of corn starch and place it in a three-necked flask. Add 35 mL of 10% hydrochloric acid solution. Heat and stir the resulting starch emulsion at 60 °C for 3 h. Then use 1 M Na 2 CO 3 solution to neutralize the hydrochloric acid. When the pH is neutral, continue stirring for 30 min. Wash with deionized water 3 - 5 times to remove other impurities in the solution. Place the product after suction filtration in a drying oven at 50 °C to dry and obtain porous starch mpSt; Dissolve 13.8 g of porous starch in 20 mL of epichlorohydrin containing 0.6 mL of concentrated HCl. After stirring the mixture at 110 °C for 18 h, wash it with absolute ethanol 3 - 5 times and dry it under vacuum at 60 °C for later use; Dissolve 8.7 g of halogenated starch in 50 mL of 0.1 M sodium hydroxide, then add 10.3 g of ethylenediamine and react at 60 °C for 24 h. After the reaction, continue to wash it with absolute ethanol 3 - 5 times and dry it under vacuum at 60 °C. Then perform ball milling treatment with a ball mill to obtain porous amino starch with a smaller particle size;

[0058] S3. Preparation of porous amino starch / silylated sodium hyaluronate composite: Take 2.31 g of the silylated sodium hyaluronate obtained in step S1 and 4.69 g of the porous amino starch obtained in step S2 and place them in a beaker. Then add 50 ml of deionized water and use the ultrasonic-microwave method to mix them evenly. The ultrasonic conditions are 160 w and 5 min;

[0059] S4. Preparation of carboxymethyl cellulose: Place the waste straw in a crusher for crushing. Put 25 g of the crushed straw in a three-necked flask. Pour 6 g of sodium hydroxide and 80 ml of ethanol into the three-necked flask. Stir at 40 °C for 3 h, then add 20 ml of chloroacetic acid. Stir at 60 °C for 3 h, then add glacial acetic acid for neutralization. Continue stirring for 0.3 - 0.5 h and then filter and wash with ethanol. After drying, obtain carboxymethyl cellulose;

[0060] S5. Preparation of acrylamide-based hydrogel solution: Take 3.25 g of acrylamide AM, 0.015 g of N,N'-methylenebisacrylamide MBA, and 0.02 g of ammonium persulfate APS and place them in a beaker. Then add 3 ml of glycerol, 14 ml of PBS buffer solution, 0.62 g of curcumin, and 0.28 g of cinnamon essential oil and stir for 30 min to obtain acrylamide-based hydrogel solution;

[0061] S6. Preparation of highly coagulated water composite hydrogel: Take 1.37 g of the composite material prepared in step S3 and 1.23 g of the carboxymethyl cellulose prepared in step S4 and add them to the acrylamide-based hydrogel solution prepared in step S5. After stirring for 30 min, pour it into a PTFE mold and place it in an oven at 50 °C to obtain a highly coagulated water composite hydrogel with a highly crosslinked network; this hydrogel has a certain antibacterial effect and can be used as a medical dressing.

[0062] Comparative Example 5: Except that chloroacetic acid is not added in step S4, the other steps are the same as those in Example 3.

[0063] By testing the mass of the sample before and after complete swelling, the swelling ratio of the sample is analyzed. Figure 4 This is the swelling data graph of the gel materials prepared in Example 3 and Comparative Example 5 of the present invention. From Figure 4 it can be seen that the material prepared in Example 3 has better swelling properties because its structure contains carboxymethyl, and this functional group has good binding with functional groups such as amino and hydroxyl groups. In addition, the tight connection of this internal structure greatly improves the water absorption and moisture retention of the material.

[0064] Example 4:

[0065] S1. Preparation of modified sodium hyaluronate: Take 2.72 g of sodium hyaluronate and dissolve it in 30 ml of N,N-dimethylformamide. Slowly add 0.18 g of 1,1-dimethoxy-silane-1-acetate, then dropwise add 10 μl of hydrochloric acid with a mass fraction of 25-35 wt%, and then add 5 mg of HMCM-22 molecular sieve. Stir at 50 °C for 15 h. After the reaction is completed, pour 100-500 ml of absolute ethanol into the reaction solution. After the solution settles, wash and dry the substrate to obtain silylated sodium hyaluronate;

[0066] S2. Preparation of porous amino starch: Weigh 16 g of corn starch and place it in a three-necked flask. Add 40 mL of a 10% hydrochloric acid solution. Heat and stir the obtained starch emulsion at 60 °C for 5 h, and then use 1 M of Na 2 CO 3The solution is neutralized with hydrochloric acid. When the pH is neutral, stirring is continued for 30 min, and it is washed 3 - 5 times with deionized water to remove other impurities in the solution. The product after suction filtration is placed in a drying oven at 50 °C to obtain porous starch mpSt; 13 g of porous starch is dissolved in 20 mL of epichlorohydrin containing 0.7 mL of concentrated HCl. After the mixture is stirred at 90 °C for 16 h, it is washed 3 - 5 times with absolute ethanol and vacuum dried at 60 °C for later use; 8.6 g of halogenated starch is dissolved in 50 mL of 0.1 M sodium hydroxide, and then 10.4 g of ethylenediamine is added and reacted at 60 °C for 24 h. After the reaction, it is continuously washed 3 - 5 times with absolute ethanol and vacuum dried at 60 °C, and then ball - milled with a ball mill to obtain porous amino starch with a smaller particle size;

[0067] S3. Preparation of porous amino starch / silylated sodium hyaluronate composite material: Take 2.36 g of silylated sodium hyaluronate obtained in step S1 and 4.64 g of porous amino starch obtained in step S2 and place them in a beaker. Then add 30 ml of deionized water, and use the ultrasonic - microwave method to mix them evenly. The ultrasonic conditions are 160 w and 5 min;

[0068] S4. Preparation of carboxymethyl cellulose: The waste straw is placed in a crusher for crushing. 20 g of the crushed straw is placed in a three - necked flask, 5 g of sodium hydroxide and 60 ml of ethanol are poured into the three - necked flask. After stirring at 40 °C for 3 h, 20 ml of chloroacetic acid is added, and after stirring at 80 °C for 3 h, glacial acetic acid is added for neutralization. After continuing to stir for 0.3 h, it is filtered and washed with ethanol, and dried to obtain carboxymethyl cellulose;

[0069] S5. Preparation of acrylamide - based hydrogel solution: Take 3.25 g of acrylamide AM, 0.015 g of N,N - methylenebisacrylamide MBA, and 0.023 g of ammonium persulfate APS and place them in a beaker, then add 3 ml of glycerol, 12 ml of PBS buffer solution, 0.64 g of curcumin, and 0.26 g of cinnamon essential oil and stir for 30 min to obtain an acrylamide - based hydrogel solution;

[0070] S6. Preparation of high - coagulation water composite hydrogel: Take 1.95 g of the composite material prepared in step S3 and 1.85 g of carboxymethyl cellulose prepared in step S4 and add them to the acrylamide - based hydrogel solution prepared in step S5. After stirring for 30 min, pour it into a PTFE mold and place it in an oven at 50 °C to obtain a high - coagulation water composite hydrogel with a high cross - linked network; This hydrogel has a certain antibacterial effect and can be used as a medical dressing.

[0071] Comparative Example 6: All other steps are the same as those in Example 4, except that cinnamon essential oil is not added in step S5.

[0072] Comparative Example 7: All other steps are the same as those in Example 4, except that curcumin is not added in step S5.

[0073] Bacteriostatic test method: Take 20 μL of frozen Escherichia coli and inoculate it into the sterilized LB liquid medium, and incubate it in a biological shaker for 4 hours and 12 hours to obtain activated bacteria. Put different gels of 0.5 x 3 cm into 50 ml centrifuge tubes (the centrifuge tubes are sterilized by ultraviolet lamp), add 5 ml of sterile water and 1 ml of Escherichia coli suspension, and shake to disperse evenly. Place the centrifuge tubes containing different samples into a biological incubator for cultivation. Take out the quantitative suspension and put it into a sterile 96-well plate after 12, 24, and 36 hours of bacterial cultivation respectively, and then use a microplate reader to measure the value of the suspension at 600 nm.

[0074] Figure 5 It is a bacteriostatic data graph of the gel materials prepared in Example 4, Comparative Example 6, and Comparative Example 7 of the present invention. From Figure 5 It can be seen that: the gel material itself has no significant antibacterial effect. However, the bacteriostatic effect of Example 4 after compounding is very obvious, and Comparative Example 6 and Comparative Example 7 also have bacteriostatic effects, but their effects are weaker. This may be because there are two components, cinnamon essential oil and curcumin, in the gel of Example 4. Due to the special spatial conformation and fixation effect, the bacteriostatic effects of these two substances are greatly promoted, and the three play a significant synergistic effect.

[0075] The above-described embodiments only represent the specific implementation manners of the present invention, and the description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, any other replacement, simplification and other replacement methods made without departing from the principle of the present invention fall within the protection scope of the present invention.

Claims

1. A process for preparing a medical material with high condensation water, characterized in that: The specific synthesis steps are as follows: S1. Preparation of modified sodium hyaluronate: 1-3 g of sodium hyaluronate is dissolved in 10-50 ml of N,N-dimethylformamide, 0.1-1 g of 1,1-dimethylol-silane-1-acetate is slowly added, and then 10-50 ul of hydrochloric acid with a mass fraction of 25-35 wt% is added dropwise, and then 5-10 mg of HMCM-22 molecular sieve is added, and stirred at 30-50 °C for 5-16 h. After the reaction is completed, 100-500 ml of anhydrous ethanol is poured into the reaction solution, and the substrate is washed and dried after the solution is precipitated to obtain silanized sodium hyaluronate; S2. Preparation of porous amino starch: weigh 10-20 g corn starch and place it in a three-necked flask, add 30-40 mL of 10% hydrochloric acid solution, heat and stir the obtained starch emulsion at 50-60 °C for 3-5 h, then use 1 M Na2CO3 solution to neutralize the hydrochloric acid, and when the pH is neutral, continue stirring for 15-30 min, wash with deionized water 3-5 times to remove other impurities in the solution, and place the filtered product in a 50 °C drying oven to dry to obtain porous starch; dissolve 13-15 g porous starch in 15-20 mL epichlorohydrin containing 0.3-0.8 ml concentrated HCl, stir the mixture at 90-110 °C for 16-24 h, wash with anhydrous ethanol 3-5 times, and vacuum dry at 60 °C for standby use; dissolve 6-9 g of the product of the porous starch reaction obtained in the previous step in 50 mL 0.1 M of sodium hydroxide, then add 10-15 g of ethylenediamine and react at 60 ° C for 24 h. After the reaction is completed, continue to wash with anhydrous ethanol for 3-5 times, vacuum dry at 60 ° C, and then use a ball mill to perform ball milling to obtain porous amino starch with smaller particle size; S3. Preparation of porous amino starch / silanized sodium hyaluronate composite material: 0.5-2.5 g of silanized sodium hyaluronate obtained in step S1 and 2.5-5 g of porous amino starch obtained in step S2 are placed in a beaker, and then 30-50 ml of deionized water are added, and the two are mixed evenly using an ultrasonic-microwave method, and the ultrasonic conditions are 160 w, 5 min; S4, preparation of carboxymethyl cellulose: placing waste straw in a grinder for crushing, placing 20-30 g of the crushed straw in a three-necked flask, pouring 5-8 g of sodium hydroxide and 60-80 ml of ethanol into the three-necked flask, stirring at 40°C for 3-5 h, adding 20-30 ml of chloroacetic acid, stirring at 60-80°C for 2.5-4.5 h, adding glacial acetic acid for neutralization, continuing to stir for 0.3-0.5 h, filtering and washing with ethanol, and drying to obtain carboxymethyl cellulose; S5. Preparation of acrylamide-based hydrogel solution: 3.05-3.85 g acrylamide, 0.015-0.025 g N,N-methylenebisacrylamide and 0.02-0.03 g ammonium persulfate are placed in a beaker, and then 1-3 ml glycerol, 7-14 ml PBS buffer, 0.6-1.3 g curcumin and 0.2-0.8 g cinnamon essential oil are added and stirred for 15-30 min to obtain an acrylamide-based hydrogel solution; S6. Preparation of high coagulation water composite hydrogel: 1.3-2.6 g of the composite material prepared in step S3 and 1-2 g of carboxymethyl cellulose prepared in step S4 are added to the acrylamide-based hydrogel solution prepared in step S5, stirred for 10-30 min, poured into a PTFE mold and placed in an oven at 50° C. to obtain a high coagulation water medical material.

2. The process for preparing a medical material with high condensation water according to claim 1, characterized in that: In step S1, 2.68 g of sodium hyaluronate was dissolved in 35 ml of N,N-dimethylformamide.

3. The process for preparing a medical material with high condensation water according to claim 2, characterized in that: In the step S1, 0.53 g of 1,1-dimethylol-silane-1-acetate, 25 ul of hydrochloric acid, and 10 mg of HMCM-22 molecular sieves were added, and the mixture was stirred at 50° C. for 12 h.

4. The process for preparing a medical material with high condensation water according to claim 3, characterized in that: In step S2, 15 g corn starch was weighed, 30 mL of 10% hydrochloric acid solution was added, and the mixture was heated and stirred at 60° C. for 5 h. After the pH was neutral, stirring was continued for 20 min.

5. The process for preparing a medical material with high coagulation water according to claim 3, characterized in that: In step S2, 10 g of porous starch is dissolved in 20 mL of epichlorohydrin containing 0.6 ml of concentrated HCl, and the mixture is stirred at 110° C. for 16 h; 6 g of halogenated starch is dissolved in 50 mL of 0.1 M sodium hydroxide, and then 10 g of ethylenediamine is added and reacted at 60° C. for 24 h.

6. The process for preparing a medical material with high condensation water according to claim 5, characterized in that: In step S3, 2.13 g of the silanized sodium hyaluronate obtained in step S1 and 3.87 g of the porous amino starch obtained in step S2 are placed in a beaker, and then 50 ml of deionized water is added.

7. The process for preparing a medical material with high coagulation water according to claim 6, characterized in that: In step S4, 20 g of the crushed straw was taken, 5.6 g of sodium hydroxide and 80 ml of ethanol were added, and the mixture was stirred at 40° C. for 5 h, then 20 ml of chloroacetic acid was added, and the mixture was stirred at 65° C. for 4 h. After neutralization, the mixture was stirred for 0.4 h.

8. The process for preparing a medical material with high coagulation water according to claim 7, characterized in that: In step S5, 3.65 g acrylamide, 0.023 g N,N-methylenebisacrylamide and 0.027 g ammonium persulfate were placed in a beaker, and then 2 ml glycerol, 13 ml PBS buffer, 0.75 g curcumin and 0.3 g cinnamon essential oil were added, and stirred for 30 min.

9. The process for preparing a medical material with high condensation water according to claim 8, characterized in that: In step S6, 2.5 g of the composite material prepared in step S3 and 2 g of the carboxymethyl cellulose prepared in step S4 are added to the acrylamide-based hydrogel solution prepared in step S5, and stirred for 30 min.

10. A medical material with high coagulation water obtained by any one of the preparation processes of claims 1 to 9.

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