Polysaccharide-based hemostatic sponge material for rapid hemostasis of deep wound cavity and preparation method of polysaccharide-based hemostatic sponge material

Abstract

The invention provides a polysaccharide-based hemostatic sponge material for rapid hemostasis of a deep wound cavity and a preparation method of the polysaccharide-based hemostatic sponge material. The problems that a hemostatic porous material prepared in the prior art is difficult to expand rapidly, poor in hydrophilicity, low in shape recovery rate, large in pores, uneven in pores, low in elastic modulus, poor in compression cycle performance and the like are solved. According to the preparation method, natural polysaccharide is adopted as a raw material, and the porous material which can absorb liquid and expand quickly, and is high in hydrophilicity, good in biocompatibility, high in shape recovery rate, small and uniform in pores, high in elasticity modulus and good in compression cycle performance is prepared through the aging salting-out method and the processes of alkalization, esterification, mixing, aging and forming.

Description

Technical Field

[0001] The present invention belongs to the technical field of hemostatic material research and development, and particularly relates to a polysaccharide-based hemostatic sponge material for rapid hemostasis in deep wound cavities and a preparation method thereof. This material can cope with bleeding in deep wound cavities and can rapidly expand for hemostasis. Background Art

[0002] In traumatic injuries, bleeding is one of the main causes of death, and bleeding in deep wound cavities is particularly dangerous. This type of bleeding mostly occurs in the trunk, large blood vessels or visceral injury sites. Due to the special anatomical structure and blood vessel distribution characteristics, traditional hemostatic methods such as tourniquets are difficult to work effectively. In first aid and trauma treatment, the timeliness of bleeding control is crucial. According to statistics, most traumatic deaths occur within the first hour after trauma, which makes the development of rapid and effective hemostatic materials become the research focus in the field of current emergency medicine.

[0003] Currently, the commonly used hemostatic materials in clinics mainly include powders, gauzes, hydrogels, sponges and other types. However, these traditional materials have obvious limitations in dealing with bleeding in deep wound cavities: ordinary sponges and gauzes are difficult to adapt to irregular characteristics and cannot effectively reach the deep bleeding sites; hemostatic powders often cannot form stable blood clots and are easily dissolved in the blood under the washing of blood, resulting in poor hemostatic effects on arterial and venous bleeding; while sticky hydrogels can form a physical barrier, but generally have problems such as low biocompatibility, slow adhesion formation, and poor mechanical matching with tissues. Especially in the blood environment, the adhesion strength between them and the tissue surface is significantly reduced.

[0004] In contrast, expandable hemostatic materials show unique advantages. These materials can rapidly expand at the trauma site, adaptively fill wounds of various shapes and depths, and promote blood coagulation through physical compression to achieve rapid hemostasis. Currently, the raw materials used to prepare expandable hemostatic materials mainly include chitosan, sodium carboxymethyl polysaccharide, gelatin, starch, etc. Among them, chitosan has attracted much attention due to its excellent hemostatic performance and good biocompatibility, and is widely used in the preparation of porous hemostatic materials. However, existing chitosan-based hemostatic materials still have obvious deficiencies: problems such as slow water absorption and expansion rate, poor hydrophilicity, and low shape recovery rate restrict their hemostatic effects. In terms of preparation processes, currently mainly phase separation method, foaming method, freeze-drying method and template method and other technologies are used to prepare hemostatic porous materials. Although these methods have their own characteristics, the prepared hemostatic porous materials generally have problems such as uneven pores, large pores, low elastic modulus, and poor compression cycle performance, and it is difficult to achieve precise control of the pore structure, which affects the hemostatic performance and mechanical properties of the materials and limits their application effects in bleeding in deep wound cavities.

[0005] In view of the above problems, it is necessary to explore a new hemostatic porous material and its preparation method, which can be used for rapid hemostasis in deep wound cavities. Summary of the Invention

[0006] The purpose of the present invention is to solve the problems that the hemostatic porous materials prepared by the existing technologies are difficult to achieve rapid swelling, have poor hydrophilicity, low shape recovery rate, large and uneven pores, low elastic modulus, and poor compression cycle performance, and to provide a polysaccharide-based hemostatic sponge material for rapid hemostasis in deep wound cavities and its preparation method.

[0007] To achieve the above purpose, the technical solution provided by the present invention is as follows:

[0008] A preparation method of a polysaccharide-based hemostatic sponge material is characterized in that it includes the following steps:

[0009] 1) Alkalization

[0010] Soak the polysaccharide in an excessive amount of alkali solution and hydrolyze it to obtain alkalized polysaccharide.

[0011] 2) Esterification

[0012] Mix the alkalized polysaccharide obtained in step 1) with carbon disulfide to carry out a xanthation reaction to obtain a mixture containing xanthated polysaccharide; this reaction is very easy and can be carried out under a vacuum, air or inert gas atmosphere, and the reaction temperature can be any temperature between 0-50°C, and the whole reaction process can be carried out with or without stirring.

[0013] 3) Mixing

[0014] Add an inorganic salt hydrate with a salting-out effect to the mixture obtained in step 2) and mix evenly to obtain a fluid precursor.

[0015] 4) Aging

[0016] Let the precursor obtained in step 3) stand for aging (i.e., carry out aging salting-out) until the fluidity of the precursor decreases to form a gel-like substance.

[0017] 5) Molding

[0018] Heat and mold the gel obtained in step 4), and then obtain the polysaccharide-based hemostatic sponge material through soaking and washing, compression molding, and drying.

[0019] Furthermore, in step 1), the polysaccharide is one or a combination of wood fiber, bamboo fiber, cotton fiber, sugarcane bagasse pulp, grass pulp, lignin, and starch;

[0020] The alkali solution is a sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium bicarbonate or sodium carbonate solution with a mass fraction of 5%-20%.

[0021] The dosage of the lye is 10 - 50 times the mass of the polysaccharide;

[0022] The soaking time is 0.1 - 24 hours.

[0023] Further, in step 1), after the hydrolysis is completed, the excessive lye is removed by suction filtration to obtain alkalized polysaccharide.

[0024] Further, in step 2), the dosage of the alkalized polysaccharide is 2 - 8 times the mass of the polysaccharide in step 1);

[0025] The dosage of carbon disulfide is 0.5 - 10 times the mass of the alkalized polysaccharide. Excessive carbon disulfide has no effect on this reaction, and the excessive carbon disulfide does not participate in the reaction. However, in order to reduce the carbon disulfide entering the subsequent steps, it is best to control its dosage within this range;

[0026] The xanthation reaction time is 5 - 72 hours.

[0027] Further, in step 3), the inorganic hydrate with salting - out effect is sodium sulfate hydrate, sodium citrate hydrate, potassium sulfate hydrate, cesium sulfate hydrate, cesium carbonate hydrate, sodium carbonate hydrate or potassium carbonate hydrate;

[0028] The dosage of the inorganic hydrate is 2 - 15 times the mass of the mixture containing xanthated polysaccharide.

[0029] Further, in step 4), the standing and aging time is 10 - 80 minutes.

[0030] Further, in step 5), the heating temperature is 40 - 98 °C; the heating time is 0.5 - 72 hours;

[0031] Soaking and cleaning are carried out successively with deionized water and ethanol, that is, first soaking and cleaning with deionized water. At this time, the pores of the material are filled with water. In order to facilitate compression molding and better shape recovery after liquid absorption, ethanol is used here to displace the water in the pores.

[0032] Meanwhile, the present invention also provides a polysaccharide - based hemostatic sponge material prepared by the above - mentioned preparation method, and the application of the polysaccharide - based hemostatic sponge material in the preparation of a hemostatic material for deep wound cavity bleeding. This material has the advantages of high hydrophilicity, good cyclic compression performance, and rapid expansion after absorbing liquid (such as water, blood, etc.) when fixed in shape under external force compression.

[0033] Based on the above application, the present invention also provides a hemostatic medical material made of the above - mentioned polysaccharide - based hemostatic sponge material, which can deal with deep wound cavity bleeding.

[0034] The concept and principle of the present invention:

[0035] In view of the technical problems existing in the prior art, the present invention starts from the two aspects of raw material selection and preparation process to explore ultra-fast expansion materials that can cope with deep wound cavity bleeding.

[0036] Natural polysaccharides have excellent biocompatibility and environmental friendliness. As one of the most abundant organic polymers in nature, they are not only widely available, but also have excellent biodegradability, which can reduce the burden on the ecological environment. In addition, the biological inertness of polysaccharides does not cause obvious immune reactions when they come into contact with human tissues, making them very suitable for preparing medical materials and helping to improve the safety and comfort of patients. On the other hand, polysaccharides represented by cellulose have the potential to undergo xanthogenic reaction with carbon disulfide, and the resulting products are unstable. They will precipitate at a certain temperature (i.e., the molding heating temperature) and under the action of inorganic salt hydrates with salting-out effect, and regenerate polysaccharides, as shown in the following formula. Therefore, the present invention intends to use natural polysaccharides as the substrate of ultra-fast expansion materials.

[0037]

[0038] Porosity is a key property that ensures the rapid absorption and hemostasis capabilities of ultra-fast swelling materials. The porous structure provides a large surface area, allowing the material to absorb a large amount of liquid in a short period of time and expand rapidly to fill the wound. The uniform distribution of pores is also crucial to the performance of the material, ensuring the consistency of the absorption rate and avoiding local uneven expansion during the absorption process, thereby improving the reliability and effectiveness of hemostasis. The uniform pore structure can also provide more stable physical support to prevent the material from breaking or failing during use. Therefore, in the process of processing natural polysaccharides into ultra-fast swelling materials, the porosity of the target product and the uniformity of the pore structure should be ensured through the preparation process.

[0039] Good mechanical properties are the basis for ensuring that ultra-fast expansion materials can play an effective role in practical applications. After absorbing liquid and swelling, the material needs to maintain sufficient mechanical strength to resist internal and external pressure and tearing, ensuring a stable hemostatic barrier at critical moments. If the material is easily deformed or ruptured when subjected to stress, it may lead to reduced hemostatic effect. Therefore, by optimizing the fiber structure and pore characteristics of the material, its mechanical properties can be effectively improved to ensure its effectiveness in various environments.

[0040] In summary, the development of ultra-fast expansion materials to deal with deep wound cavity bleeding should combine the superior biocompatibility and environmental friendliness of natural polysaccharides while giving the material a rich and uniform porous morphology, excellent mechanical properties and fluid absorption capacity, providing a new efficient, safe and environmentally friendly option for controlling deep wound cavity bleeding.

[0041] To this end, the present invention provides a liquid-absorbing ultra-rapidly expanding porous material (i.e., polysaccharide-based hemostatic sponge material) capable of dealing with deep wound cavity bleeding and a preparation method thereof. Using the aging salting-out method, polysaccharide is used as the raw material for preparing the hemostatic porous material. First, the polysaccharide is hydrolyzed and extracted in an alkaline solution to obtain alkalized polysaccharide; secondly, the alkalized polysaccharide is reacted with carbon disulfide to obtain a mixture containing xanthated polysaccharide; then the mixture containing xanthated polysaccharide is mixed with an inorganic salt hydrate having a salting-out effect to obtain a flowable precursor; thereafter, the precursor is aged to obtain a gel; subsequently, it is heated to form a porous material, and finally becomes a liquid-absorbing rapidly expanding porous material - polysaccharide-based hemostatic sponge material through soaking and washing, compression molding, and drying.

[0042] In the above preparation process, the aging salting-out method is mainly used. The polymer solution is mixed with the salt hydrate, and the aggregation of hydrophilic polymer chains is regulated at the molecular level through the Hofmeister effect, so as to prepare a porous material with excellent mechanical properties to meet the urgent needs in this field, which is completely different from the research results of previous researchers on the ion-specific effect of hydrophilic polymers. Different salts show different abilities to precipitate proteins from aqueous solutions, which is called the Hofmeister effect or ion-specific effect; previous studies have shown that the ion-specific effect is caused by the influence of different ions on the hydration water around the hydrophilic functional groups on the hydrophobic chain; for natural macromolecules, a large number of researchers have studied the influence of different ions on the solubility and swelling of polymers under the influence of this effect; a few literature reports a method of improving the mechanical properties of hydrogels by soaking them in salt solutions after hydrogel synthesis; however, there is currently no study showing the influence of ions on the mechanical properties of porous materials prepared from hydrogels and the shaping of porous materials.

[0043] The beneficial effects of the present invention are as follows:

[0044] 1. The present invention provides a method for preparing a high-performance polysaccharide-based hemostatic sponge material based on the aging salting-out method. Through alkalization, esterification, mixing, aging, and shaping processes, a polysaccharide-based hemostatic sponge material with liquid-absorbing rapid expansion, high hydrophilicity, excellent biocompatibility, high shape recovery rate, small and uniform pores, high elastic modulus, and good compression cycle performance is successfully prepared.

[0045] 2. The present invention realizes the precise control of the microstructure of the material by introducing a room-temperature aging salting-out process to regulate the fluidity of the precursor and the molecular aggregation behavior. During the aging salting-out process, the high-concentration salt solution destroys the hydration layer on the surface of the polar molecular chains, prompting the molecular chains to aggregate and crystallize, forming a stable gel network structure. This process not only significantly improves the mechanical properties of the material but also effectively avoids the generation of large-size pores due to the rapid evaporation of water during the heat-forming process by reducing the fluidity of the precursor. Finally, a hemostatic porous material with the advantages of uniform and fine pore structure, high elastic modulus, excellent compression cycle performance, fast liquid absorption and swelling rate, high shape recovery rate, etc. is obtained. These characteristics enable the material to better adapt to the irregular wound morphology, quickly fill the deep wound cavity, and achieve effective hemostasis.

[0046] 3. The material prepared by the present invention also exhibits good biocompatibility and degradation performance, meeting the safety requirements for clinical use; by regulating the aging salting-out process parameters, the pore structure and mechanical properties of the material can be controlled; this method has the advantages of simple process, low cost, easy large-scale production, etc., providing a new technical approach for the development of a new generation of highly efficient hemostatic materials. Description of the Drawings

[0047] Figure 1 SEM images of the cross-sections of the polysaccharide-based hemostatic sponge materials prepared with aging salting-out times of 0 minutes and 20 minutes in Example 1; a and b are the SEM images of the material with an aging salting-out time of 0 minutes, and c and d are the SEM images of the material with an aging salting-out time of 20 minutes.

[0048] Figure 2 Compressive stress-strain relationship diagrams (a) and compressive modulus diagrams (b) of the polysaccharide-based hemostatic sponge materials prepared with salting-out times of 0, 10, 20, 40, and 80 minutes.

[0049] Figure 3 Images of the cross-sections of the polysaccharide-based hemostatic sponge materials prepared with salting-out times of 0 and 20 minutes.

[0050] Figure 4 Cyclic compressive stress-strain relationship diagrams and digital photos of the polysaccharide-based hemostatic sponge materials prepared in Example 3.

[0051] Figure 5 Cyclic compressive modulus diagram of the polysaccharide-based hemostatic sponge materials prepared in Example 3.

[0052] Figure 6 Relationship diagrams of the deformation recovery rate and water absorption rate of the polysaccharide-based hemostatic sponge materials prepared in Example 4 varying with the compressive strain.

[0053] Figure 7Graph showing the relationship between the deformation recovery rate of the polysaccharide-based hemostatic sponge material prepared in Example 4 and the number of cycles.

[0054] Figure 8 Results of the hemolysis experiment and cytotoxicity experiment of the polysaccharide-based hemostatic sponge material prepared in Example 6. Detailed implementation manners

[0055] The present invention will be further described below in conjunction with specific embodiments. The experimental methods used in the following embodiments are all conventional methods unless otherwise specified. The materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained by those skilled in the art through commercial channels without special instructions.

[0056] Example 1:

[0057] A method for preparing a polysaccharide-based hemostatic sponge material is as follows:

[0058] 1) Weigh 3 g of lignin into a 250 mL glass beaker, add 90 mL of sodium hydroxide solution with a mass fraction of 20%, mix evenly and soak for 2 hours to obtain an alkalized polysaccharide mixture containing excess alkali solution. Filter the mixture to remove the excess sodium hydroxide solution until 12 g of alkalized polysaccharide is obtained.

[0059] 2) Add 16 g of carbon disulfide to the alkalized polysaccharide and react at 25 °C for 36 hours to obtain a mixture containing xanthated polysaccharide.

[0060] 3) Mix the mixture containing xanthated polysaccharide and sodium sulfate decahydrate evenly according to a mass ratio of 1:10, and let it stand at room temperature for 20 minutes to obtain a gel.

[0061] 4) After heating the gel at 90 °C for 24 hours to form a shape, soak it in deionized water for 24 hours, wash to remove the excess sodium sulfate and by-products, then soak it in ethanol for a period of time to displace the water, and finally compress, shape and dry it at 60 °C to obtain the polysaccharide-based hemostatic sponge material.

[0062] Comparative Example 1

[0063] The difference from Example 1 is as follows:

[0064] In step 3), after mixing the mixture containing xanthated polysaccharide and sodium sulfate decahydrate evenly according to a mass ratio of 1:10, directly proceed to step 4), that is, the aging and salting-out time is 0 minutes.

[0065] The present invention compared the products obtained in Example 1 and Comparative Example 1:

[0066] Figure 1SEM images of the cross-section of the polysaccharide-based hemostatic sponge material (also known as porous material) prepared with an aging salting-out time of 0 minutes (a, b) and an aging salting-out time of 20 minutes (c, d). As can be seen from Figure 1 It can be seen that the SEM cross-section of the porous material with an aging salting-out time of 0 minutes (a, b) shows a porous morphology, and the fibers forming the pores are arranged uniformly and without orientation. However, the SEM cross-section of the porous material with an aging salting-out time of 20 minutes (c, d) shows an arranged pattern with a certain orientation. This may be because during the salting-out process, under the Hofmeister effect, the bound water on the surface of the hydrophilic polysaccharide is transformed into free water, and the hydrophilic polysaccharide further aggregates and becomes oriented.

[0067] Meanwhile, the present invention also conducted the same examples as in Example 1, with the difference that the standing time (i.e., the aging salting-out time) in step 3) was 10, 40, and 80 minutes in sequence, and comparisons were made with Example 1 and Comparative Example 1. Figure 2 Graphs of the compressive stress-strain relationship (a) and compressive modulus (b) of the polysaccharide-based hemostatic sponge materials prepared with salting-out times of 0, 10, 20, 40, and 80 minutes respectively. It can be seen that as the aging salting-out time increases, the compressive modulus of the polysaccharide-based hemostatic sponge material shows a trend of first increasing and then decreasing. The maximum compressive modulus is for the porous material prepared with an aging salting-out time of 20 minutes (14.07 KPa), which is 3.27 times that of the porous material prepared with an aging salting-out time of 0 minutes (4.3 KPa). This is mainly attributed to the fact that the aging salting-out process causes the fibers to aggregate, thus generating an orientation effect. With the further extension of the aging salting-out time, it can be seen that the compressive modulus of the polysaccharide-based hemostatic sponge material decreases. This may be due to the premature precipitation of xanthate caused by too long an aging salting-out time.

[0068] Figure 3 Images of the cross-sections of the porous materials prepared with salting-out times of 0 and 20 minutes. The image on the left is the cross-section image of the product of Comparative Example 1, and the image on the right is the cross-section image of the product of Example 1. It can be seen that the internal pores of the porous material with an aging salting-out time of 20 minutes are significantly smaller than those of the porous material with an aging salting-out time of 0 minutes.

[0069] Example 2:

[0070] A preparation method of a polysaccharide-based hemostatic sponge material is as follows:

[0071] 1) Weigh 3 g of bamboo fibers into a 250 mL glass beaker, add 30 mL of a sodium bicarbonate solution with a mass fraction of 20%, mix evenly and soak for 10 hours to obtain an alkalized polysaccharide mixture containing excess alkali solution. Filter the mixture to remove the excess sodium hydroxide solution until 12 g of alkalized polysaccharide is obtained.

[0072] 2) Add 6 g of carbon disulfide to the alkalized polysaccharide and react at 25 °C for 36 hours to obtain a mixture containing xanthated polysaccharide.

[0073] 3) Mix the mixture containing xanthated polysaccharide and sodium sulfate decahydrate evenly according to a mass ratio of 1:5 and let it stand at room temperature for 20 minutes to obtain a gel.

[0074] 4) After the gel is heated at 40 °C for 72 hours to form a shape, soak it in deionized water for 24 hours, wash to remove excess sodium sulfate and by-products, then soak it in ethanol for a period of time to displace the water, and finally compress, shape and dry it at 60 °C to obtain the polysaccharide-based hemostatic sponge material.

[0075] Example 3:

[0076] A method for preparing a polysaccharide-based hemostatic sponge material is as follows:

[0077] 1) Weigh 3 g of wood fibers into a 250 mL glass beaker, add 150 mL of a 10% sodium hydroxide solution by mass fraction, mix evenly and soak for 24 hours to obtain an alkalized polysaccharide mixture containing excess alkali solution. Filter the mixture to remove the excess sodium hydroxide solution until 48 g of alkalized polysaccharide is obtained.

[0078] 2) Add 48 g of carbon disulfide to the alkalized polysaccharide and react at 25 °C for 36 hours to obtain a mixture containing xanthated polysaccharide.

[0079] 3) Mix the mixture containing xanthated polysaccharide and sodium sulfate decahydrate evenly according to a mass ratio of 1:8 and let it stand at room temperature for 20 minutes to obtain a gel.

[0080] 4) Heat the gel at 98 °C for 0.5 hour to form a shape, soak it in deionized water for 48 hours, wash to remove excess sodium sulfate and by-products, then soak it in ethanol for a period of time to displace the water, and finally compress, shape and dry it at 60 °C to obtain the polysaccharide-based hemostatic sponge material.

[0081] Figure 4The figure is a cyclic compression stress-strain relationship diagram and digital photo of the polysaccharide-based hemostatic sponge material prepared in Example 3. It can be seen that the stress-strain curve of the porous material during the compression process after absorbing liquid can be roughly divided into two stages. The first stage is the strain of 0-70%. During this stage, the stress of the porous material during the compression process roughly shows a linear change with the strain. This is because the relatively uniform pores inside the porous material are caused during the compression and folding process. As the compression deformation further deepens to more than 80%, the stress of the porous material still shows a linear change with the strain, but the difference is that the modulus is significantly improved. This may be because in addition to the larger pores, there are smaller pores and capillaries in the porous material. In addition, in the case of 10 cycles, the stress-strain curves of the porous material are basically overlapped, which shows that the porous material prepared by the present invention has good compression cyclicity. Figure 5 This is a graph of the cyclic compression modulus of the polysaccharide-based hemostatic sponge material prepared in Example 3. It can be seen that during the cycle, the compression modulus of the porous material does not decrease significantly, further proving the good compression cycle performance of the porous material.

[0082] Embodiment 4:

[0083] A method for preparing a polysaccharide-based hemostatic sponge material is as follows:

[0084] 1) Weigh 3 g of starch into a 250 mL glass beaker, add 60 mL of 20% sodium hydroxide solution, mix well and soak for 0.1 hour to obtain an alkalized polysaccharide mixture containing excess alkali solution, and filter the mixture to remove excess sodium hydroxide solution until the alkalized polysaccharide is 12 g.

[0085] 2) Add 12 g of carbon disulfide to the alkalized polysaccharide and react at 25° C. for 5 hours to obtain a mixture containing xanthated polysaccharide.

[0086] 3) The mixture containing the xanthated polysaccharide and sodium sulfate decahydrate were uniformly mixed in a mass ratio of 1:15, and allowed to stand at room temperature for 20 minutes to obtain a gel.

[0087] 4) After the gel is heated at 60° C. for 48 hours to be formed, it is immersed in deionized water for 24 hours to wash away excess sodium sulfate and by-products, and then immersed in ethanol for a period of time to replace the water. Finally, it is compressed and dried at 60° C. to obtain a polysaccharide-based hemostatic sponge material.

[0088] The water absorption content of the polysaccharide-based hemostatic sponge material when expanded in deionized water was tested. The compressed polysaccharide-based hemostatic sponge material (m0) was placed in deionized water at room temperature for 20 minutes. The polysaccharide-based hemostatic sponge material was clamped with tweezers and placed in the air for 1 minute to remove the excess liquid attached to the surface of the polysaccharide-based hemostatic sponge material, and then weighed (mw )。The water absorption rate (WR) is calculated according to the following formula, and the results are shown in Figure 6 。

[0089]

[0090] The shape recovery performance of the porous material was measured to evaluate its shape memory ability. The original length of the prepared cylindrical porous material (with a diameter of about 10 mm) was L1, and the compressed height was set as L2. Then, after soaking it in deionized water for 30 seconds, the height of the porous material was measured as L3. The expansion rate of the porous material was calculated according to the following formula, and the results are shown in Figure 6 。

[0091]

[0092] It can be seen that below 80% compressive strain, the porous material has an extremely high deformation recovery rate (the deformation recovery rate is close to 100%). However, when the strain exceeds 80%, the strain recovery rate drops rapidly. This may be due to the fact that under a large strain, the microporous structure of the porous material is compressed or even damaged, resulting in plastic deformation. In addition, below 80% compressive strain, the porous material has an extremely high water absorption rate (the water absorption rate exceeds 1650% in all cases), which is due to the porous structure and high hydrophilicity of the material.

[0093] Figure 7 It is a graph showing the relationship between the deformation recovery rate of the polysaccharide-based hemostatic sponge material prepared in Example 4 and the number of cycles. It can be seen that under multiple compression cycles, the deformation recovery rate of the porous material does not decrease significantly, indicating that the prepared porous material has extremely strong compression cycle shape recovery performance.

[0094] Example 5:

[0095] A preparation method of a polysaccharide-based hemostatic sponge material is as follows:

[0096] 1) Weigh 3 g of bagasse pulp into a 250 mL glass beaker, add 120 mL of sodium hydroxide solution with a mass fraction of 20%, mix evenly and soak for 12 hours to obtain an alkalized polysaccharide mixture containing excess alkali solution. Filter the mixture to remove the excess sodium hydroxide solution until 12 g of alkalized polysaccharide is obtained.

[0097] 2) Add 20 g of carbon disulfide to the alkalized polysaccharide and react at 25 °C for 36 hours to obtain a mixture containing xanthated polysaccharide.

[0098] 3) Mix the mixture containing xanthated polysaccharide and sodium sulfate decahydrate evenly according to a mass ratio of 1:20, and let it stand at room temperature for 20 mins to obtain a gel.

[0099] 4) After the gel is heated at 72 °C for 36 hours to form, it is soaked in deionized water for 24 hours to wash away the excess sodium sulfate and by-products. Subsequently, it is soaked in ethanol for a period of time to displace the water, and finally, it is compression-molded and dried at 60 °C to obtain the polysaccharide-based hemostatic sponge material.

[0100] Example 6:

[0101] A preparation method of a polysaccharide-based hemostatic sponge material is as follows:

[0102] 1) Weigh 3 g of cotton fiber into a 250 mL glass beaker, add 90 mL of sodium hydroxide solution with a mass fraction of 20%, mix evenly and soak for 24 hours to obtain an alkalized polysaccharide mixture containing excess lye. Filter the mixture to remove the excess sodium hydroxide solution until 12 g of alkalized polysaccharide is obtained.

[0103] 2) Add 48 g of carbon disulfide to the alkalized polysaccharide and react at 25 °C for 72 hours to obtain a mixture containing xanthated polysaccharide.

[0104] 3) In order to obtain porous materials with different densities, the mixture containing xanthated polysaccharide and sodium sulfate decahydrate are mixed evenly according to the mass ratios of 1:3, 1:5, 1:7, and 1:10 respectively, and left to stand at room temperature for 20 minutes to obtain a gel.

[0105] 4) After each gel is heated at 90 °C for 3 hours to form, it is soaked in deionized water for 24 hours to wash away the excess sodium sulfate and by-products. Subsequently, it is soaked in ethanol for a period of time to displace the water, and finally, it is compression-molded and dried at 60 °C respectively to obtain polysaccharide-based hemostatic sponge materials with different densities.

[0106] Figure 8 Blood compatibility (a) and cytotoxicity test results (b, c) of porous materials prepared with different ratios of the mixture containing xanthated polysaccharide and sodium sulfate decahydrate; it can be seen that the hemolysis rate of the prepared materials is less than 5%, and there is no cytotoxicity, and the use safety is high.

[0107] In summary, it can be seen that the polysaccharide-based hemostatic sponge material prepared by the present invention has high hydrophilicity, a high shape recovery rate, can adapt to various trauma shapes and depths, fill irregular wounds, has the performance of dealing with deep wound cavity bleeding, and can be used as a hemostatic material for deep wound cavity bleeding.

[0108] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should all be covered within the protection scope of the present invention.

Claims

1. A preparation method of a polysaccharide-based hemostatic sponge material, characterized in that, It includes the following steps: 1) Alkalinization Soak the polysaccharide in an excessive amount of alkaline solution and hydrolyze it to obtain alkalized polysaccharide; 2) Esterification Mix the alkalized polysaccharide obtained in step 1) with carbon disulfide to carry out xanthation reaction to obtain a mixture containing xanthated polysaccharide; 3) Mixing materials Add an inorganic hydrate with salting-out effect to the mixture obtained in step 2) and mix evenly to obtain a fluid precursor; 4) Aging Let the precursor obtained in step 3) stand for aging until a gel body is formed; 5) Molding and compression After heating and molding the gel body obtained in step 4), soak, wash, compress and shape, and dry it to obtain a polysaccharide-based hemostatic sponge material.

2. The preparation method according to claim 1, wherein: In step 1), the polysaccharide is one or a combination of wood fiber, bamboo fiber, cotton fiber, bagasse pulp, grass pulp, lignin and starch; The alkaline solution is a sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium bicarbonate or sodium carbonate solution with a mass fraction of 5%-20%; The dosage of the alkaline solution is 10-50 times the mass of the polysaccharide; The soaking time is 0.1-24 hours.

3. The preparation method according to claim 1 or 2, wherein: In step 1), after hydrolysis is completed, filter by suction to remove the excessive alkaline solution to obtain alkalized polysaccharide.

4. The preparation method according to claim 3, wherein: In step 2), the dosage of carbon disulfide is 0.5-10 times the mass of the alkalized polysaccharide; The xanthation reaction time is 5-72 hours.

5. The preparation method according to claim 4, wherein: In step 3), the inorganic hydrate with salting-out effect is sodium sulfate hydrate, sodium citrate hydrate, potassium sulfate hydrate, cesium sulfate hydrate, cesium carbonate hydrate, sodium carbonate hydrate or potassium carbonate hydrate; The dosage of the inorganic hydrate is 2-15 times the mass of the mixture containing xanthated polysaccharide.

6. The preparation method according to claim 5, wherein: In step 4), the standing and aging time is 10-80 minutes.

7. The preparation method according to claim 6, wherein: In step 5), the heating temperature is 40-98 °C; the heating time is 0.5-72 hours; Soak and wash successively with deionized water and ethanol.

8. A polysaccharide-based hemostatic sponge material, characterized in that: Prepared by using the preparation method according to any one of claims 1-7.

9. Application of the polysaccharide-based hemostatic sponge material according to claim 8 in the preparation of a hemostatic material for deep wound cavity bleeding.

10. A material for rapid hemostasis of deep wound cavities, characterized in that: Its material is the polysaccharide-based hemostatic sponge material according to claim 8.

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