Chitosan hemostatic sponge material and preparation method thereof

Abstract

The application provides a chitosan hemostatic sponge material and a preparation method thereof, and the method comprises the following steps: adding an emulsifier into polyvinyl alcohol water solution, and stirring under heating to obtain a polyvinyl alcohol mixture; adding carboxylated chitosan fibers and chitosan into acetic acid water solution to obtain a chitosan mixed solution; adding a crosslinking agent into the polyvinyl alcohol mixture, and then adding the chitosan mixed solution to obtain a crosslinking solution; pouring the crosslinking solution into a film forming device, and performing freeze vacuum drying to obtain the chitosan hemostatic sponge material. In the application, the carboxylated fibers are used as a reinforced framework, the PVA is used as a flexible toughening phase, and the chitosan is used as an active functional phase; the carboxylated chitosan fibers are uniformly dispersed in the PVA / chitosan matrix to form a three-dimensional fiber network framework, so that the tensile strength and the compression resistance of the sponge are significantly improved, and the defects that the components are prone to phase separation and the fibers are prone to falling off in the traditional physical mixing system are solved.

Description

Technical Field

[0001] This invention relates to the field of hemostatic sponge technology, and in particular to a chitosan hemostatic sponge material and its preparation method. Background Technology

[0002] Chitosan is a natural alkaline aminopolysaccharide polymer extracted from shrimp, crab, and other shellfish. Due to its unique bioactivities, such as alkalinity, high biocompatibility, promotion of hemagglutination, tissue adhesion, antibacterial properties, immune-boosting effects, non-toxicity, low allergenicity, and antioxidant capacity, chitosan (CS) has been widely used in materials engineering and biomedicine. In medical materials, the slow degradation of chitosan can stimulate fibroblast proliferation, which helps collagen aggregation and hyaluronic acid synthesis at the wound site, accelerating wound healing and preventing scab formation. In addition, chitosan's antibacterial properties are also one of the important reasons for its use as a common hemostatic material.

[0003] However, existing chitosan hemostatic sponge materials still have the following technical problems: Pure chitosan sponges are brittle and have poor toughness, making them prone to breakage during clinical operations. This makes them unsuitable for packing deep wounds or complex injuries, limiting their reliability in practical applications. The bond between chitosan and carrier materials is not strong. When chitosan is combined with other carrier materials, chitosan may detach from the material and enter the body during hemostasis, posing a risk of thrombosis and also leading to unstable hemostatic effects. Summary of the Invention

[0004] This invention addresses the technical problems of existing chitosan hemostatic sponges, such as insufficient mechanical properties, easy shedding of chitosan, and limited hemostatic effect, by providing a chitosan hemostatic sponge material and its preparation method.

[0005] Specifically, a method for preparing a chitosan hemostatic sponge material includes the following steps: An emulsifier is added to an aqueous polyvinyl alcohol solution, and the mixture is heated and stirred to obtain a polyvinyl alcohol mixture. Carboxylated chitosan fibers and chitosan were added to an aqueous acetic acid solution to obtain a chitosan mixed solution; A crosslinking agent is added to a polyvinyl alcohol mixture, followed by a chitosan mixture to obtain a crosslinking solution. The crosslinking solution was poured into a film-forming device and freeze-dried under vacuum to obtain chitosan hemostatic sponge material.

[0006] Aqueous polyvinyl alcohol (PVA) is blended with an emulsifier to form a stable continuous phase. Carboxylated chitosan fibers are co-dispersed with chitosan in an aqueous acetic acid solution. Under acidic conditions, the amino groups of chitosan are protonated, acquiring positive charge and water solubility, while the carboxylated fibers carry a negative charge through their surface carboxyl groups (-COOH). When the PVA mixture is mixed with a crosslinking agent, the crosslinking agent molecules act as "molecular bridges," reacting with the hydroxyl groups (-OH) of PVA and the amino groups (-NH2) of chitosan to form a preliminary chemical crosslinking network. Subsequently, when the chitosan mixture is added, a triple crosslinking reaction occurs in the system: the crosslinking agent continues to bridge PVA and chitosan to form a covalent / hydrogen bond network; the -COO⁻ on the surface of the carboxylated fibers and the -NH3⁺ on the surface of chitosan undergo electrostatic attraction, forming ionic crosslinks; and numerous intermolecular hydrogen bonds are formed between the hydroxyl groups of PVA, the amino groups of chitosan, and the carboxyl groups of the fibers. This triple crosslinking mechanism works synergistically to connect PVA, chitosan, and carboxylated fibers into a stable three-dimensional network structure. Finally, during the freeze-drying process, the solvent water crystallizes to form ice crystals. After the ice crystals sublimate under vacuum, they leave behind a continuous porous structure. The three-dimensional cross-linked network retains its skeleton integrity after the ice crystals are removed, forming a hemostatic sponge with high porosity.

[0007] Preferably, the polyvinyl alcohol (PVA) in the aqueous solution has a PVA mass fraction of 5%-10%; the emulsifier is a nonionic surfactant, accounting for 0.2%-0.5% of the PVA mixture mass. The hydrophilic polyoxyethylene segments of the nonionic surfactant (such as Tween-80) extend into the aqueous phase, while the hydrophobic segments adsorb onto the hydrophobic microregions of the PVA molecular chain or the surface of bubbles, effectively reducing the liquid-liquid and liquid-gas interfacial tension. More preferably, the PVA in the aqueous solution has a PVA mass fraction of 8%; the emulsifier is Tween-80, accounting for 0.3% of the PVA mixture mass.

[0008] Preferably, carboxylated chitosan fibers are prepared by the following steps: acrylic acid is added to anhydrous ethanol, then chitosan fibers are added, and the reaction is carried out at 60-80°C for 24-50 hours; then the mixture is washed until strongly alkaline, then washed until neutral, and finally dried to obtain carboxylated chitosan fibers. Through this preparation method, carboxyl groups (-COOH) are successfully grafted onto the surface of chitosan fibers, upgrading them from ordinary fibers to a "reactive enhanced phase." The introduction of carboxyl groups achieves two goals: first, under physiological conditions, carboxyl groups ionize to -COO⁻, which can form ionic bonds with positively charged quaternized chitosan, enhancing the interfacial bonding between the fiber and the matrix; second, carboxyl groups impart stronger hydrophilicity to the fibers, increasing the water absorption rate of the sponge. More preferably, carboxylated chitosan fibers are prepared by the following steps: acrylic acid is added to anhydrous ethanol, then chitosan fibers are added, and the reaction is carried out at 70°C for 36 hours; then the mixture is washed until strongly alkaline, then washed until neutral, and finally dried to obtain carboxylated chitosan fibers.

[0009] Preferably, the acetic acid aqueous solution has a mass fraction of 2-5%, the chitosan accounts for 1-3% of the total mass of the chitosan mixed solution, and the carboxylated chitosan fibers account for 0.5-2% of the total mass of the chitosan mixed solution. More preferably, the acetic acid aqueous solution has a mass fraction of 3%, the chitosan accounts for 2% of the total mass of the chitosan mixed solution, and the carboxylated chitosan fibers account for 1% of the total mass of the chitosan mixed solution.

[0010] Preferably, the crosslinking agent is glutaraldehyde or tannic acid, accounting for 1-3% of the mass of the polyvinyl alcohol mixture, more preferably 2%. Tannic acid belongs to plant polyphenols, and its crosslinking mechanism is as follows: a large number of ortho- and posterior phenolic hydroxyl groups in the molecule can act as hydrogen donors, forming multiple hydrogen bond crosslinking sites with the amino groups (hydrogen acceptors) of chitosan and the hydroxyl groups (hydrogen acceptors) of PVA. One tannic acid molecule can simultaneously form hydrogen bonds with multiple polymer chains, constructing a dense physical crosslinking network.

[0011] Preferably, the freeze-drying step includes: pre-freezing: pre-freezing the crosslinking solution at -40 to -20°C for 0.5-24 hours, and then freezing it at a vacuum of 1-20 Pa and a temperature of -20 to -5°C for 2-10 hours. More preferably, pre-freezing is performed at -30°C for 12 hours, followed by freeze-drying at a vacuum of 10 Pa and a temperature of -15°C for 6 hours.

[0012] Preferably, the chitosan is quaternized chitosan (QCS) or a complex of quaternized chitosan and carboxymethyl enzymatically hydrolyzed starch prepolymer electrolyte. Quaternized chitosan is produced by introducing quaternary ammonium groups onto the amino groups of the chitosan molecular chain, giving the chitosan a permanent positive charge. Unlike the amino groups of ordinary chitosan, the quaternary ammonium groups of QCS retain a positive charge under any pH conditions.

[0013] When QCS is pre-complexed with carboxymethyl hydrolyzed starch (anionic polysaccharide), the two undergo a polyelectrolyte complexation reaction under pH 6.5-7.0 conditions, forming an "ionic cross-linked network." Simultaneously, the clustered branched structure retained by the hydrolyzed starch (amylopectin characteristic) gives the complex topological entanglement capabilities—short, branched starch segments can interweave between subsequently added PVA and chitosan molecular chains. Under stress, the branched starch segments dissipate energy through slippage and stretching (sacrificial bond effect), giving the material both high strength and high toughness. Furthermore, the strong hydrophilicity of carboxymethyl hydrolyzed starch further enhances the sponge's blood absorption rate, and its negative charge synergistically improves the dispersibility of carboxylated fibers.

[0014] Preferably, quaternized chitosan is obtained through the following steps: chitosan is dissolved in acetic acid solution, then 2,3-epoxypropyltrimethylammonium chloride is added, the mixture is reacted at 40-90°C for 12-24 hours, and after purification, it is freeze-dried to obtain quaternized chitosan.

[0015] Preferably, the quaternized chitosan and carboxymethyl hydrolyzed starch prepolymer electrolyte complex is obtained through the following steps: dissolving carboxymethyl hydrolyzed starch in deionized water to obtain a starch solution, wherein the concentration of carboxymethyl hydrolyzed starch is 1-3%; then adjusting the pH to 6.5-7.0 with NaOH; dissolving quaternized chitosan in water and slowly adding it dropwise to the starch solution while stirring, wherein the mass of carboxymethyl hydrolyzed starch accounts for 2-8% of the mass of quaternized chitosan.

[0016] A chitosan hemostatic sponge material is prepared by the above-described preparation method.

[0017] The present invention has the following beneficial effects: This invention uses carboxylated fibers as a reinforcing skeleton, PVA as a flexible toughening phase, and chitosan as an active functional phase. The carboxylated chitosan fibers are uniformly dispersed in the PVA / chitosan matrix to form a three-dimensional fiber network skeleton, which significantly improves the tensile strength and compressive strength of the sponge and solves the defects of easy phase separation and easy fiber detachment in traditional physical mixing systems.

[0018] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures particularly pointed out in the written description and the accompanying drawings.

[0019] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0020] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings: Figure 1 This is a schematic flowchart illustrating the preparation method of the chitosan hemostatic sponge material of the present invention. Detailed Implementation

[0021] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0022] like Figure 1 As shown, a method for preparing a chitosan hemostatic sponge material includes the following steps: An emulsifier is added to an aqueous polyvinyl alcohol solution, and the mixture is heated and stirred to obtain a polyvinyl alcohol mixture. Carboxylated chitosan fibers and chitosan were added to an aqueous acetic acid solution to obtain a chitosan mixed solution; A crosslinking agent is added to a polyvinyl alcohol mixture, followed by a chitosan mixture to obtain a crosslinking solution. The crosslinking solution was poured into a film-forming device and freeze-dried under vacuum to obtain chitosan hemostatic sponge material.

[0023] This invention uses carboxylated fibers as a reinforcing skeleton, PVA as a flexible toughening phase, and chitosan as an active functional phase. The carboxylated chitosan fibers are uniformly dispersed in the PVA / chitosan matrix to form a three-dimensional fiber network skeleton, which significantly improves the tensile strength and compressive strength of the sponge and solves the defects of easy phase separation and easy fiber detachment in traditional physical mixing systems.

[0024] The present invention will be further described below with reference to embodiments.

[0025] All raw materials used in the embodiments of this invention are commercially available.

[0026] Polyvinyl alcohol (PVA) has a degree of polymerization of 1700±50 and a degree of alcoholysis of 98%-99%. The nonionic surfactant was Tween-80 (chemical name: polyoxyethylene sorbitan monooleate), with an HLB value of approximately 15, and was of analytical grade. Chitosan, with a degree of deacetylation of 85%-95%, a molecular weight of 100,000-300,000, and a viscosity of 50-800 mPa·s, is available in food or medical grade. Chitosan fibers with a linear density of 1.0-2.0 dtex and a length of 1-5 mm. Example 1

[0027] This embodiment provides a chitosan hemostatic sponge material and its preparation method, the specific steps of which are as follows: (1) Preparation of carboxylated chitosan fibers: 10 mL of acrylic acid was added to 100 mL of anhydrous ethanol and stirred until homogeneous. Then, 5 g of chitosan fiber was added, and the mixture was reacted at 70°C for 36 h. After the reaction was complete, the mixture was washed with deionized water until strongly alkaline (pH>10), then washed with deionized water until neutral (pH=7), and finally dried under vacuum at 50°C to obtain carboxylated chitosan fiber.

[0028] (2) Preparation of polyvinyl alcohol mixture: Polyvinyl alcohol was added to deionized water to prepare an 8% PVA aqueous solution, which was then heated to 90°C and stirred until completely dissolved. After cooling to 60°C, Tween-80 (0.3% by mass of the PVA mixture) was added and stirred until homogeneous to obtain the polyvinyl alcohol mixture.

[0029] (3) Preparation of chitosan mixed solution: Chitosan was added to a 3% (w / w) aqueous solution of acetic acid to prepare a chitosan acid solution with a 2% (w / w) chitosan content. Then, the carboxylated chitosan fibers prepared in step (1) (accounting for 1% of the total mass of the chitosan mixed solution) were added and stirred to disperse evenly to obtain a chitosan mixed solution.

[0030] (4) Preparation of crosslinking solution: Add glutaraldehyde (2% of the mass of the polyvinyl alcohol mixture) to the polyvinyl alcohol mixture obtained in step (2) and stir until homogeneous. Then add the chitosan mixture obtained in step (3) (the mass ratio of PVA to chitosan is 1:1) and stir for 30 minutes to obtain a crosslinking solution.

[0031] (5) Freeze-drying and shaping: The crosslinking solution obtained in step (4) is poured into a film forming device (mold), pre-frozen at -30°C for 12 hours, and then freeze-dried at a vacuum of 10 Pa and -15°C for 6 hours to obtain chitosan hemostatic sponge material. Example 2

[0032] The difference between this embodiment and Embodiment 1 is that in step (3), the chitosan is quaternized chitosan, and the specific preparation method is as follows: Chitosan was dissolved in a 2% acetic acid solution, and 2,3-epoxypropyltrimethylammonium chloride (GTMAC, twice the mass of chitosan) was added. The mixture was reacted at 70°C for 18 h. After the reaction was complete, the mixture was dialyzed against deionized water for 48 h and then lyophilized to obtain quaternized chitosan.

[0033] The remaining steps are the same as in Example 1. Example 3

[0034] The difference between this embodiment and embodiment 1 is that in step (4), the crosslinking agent is tannic acid, and the amount added is 2% of the mass of the polyvinyl alcohol mixture.

[0035] The remaining steps are the same as in Example 1. Example 4

[0036] This embodiment provides a chitosan hemostatic sponge material and its preparation method, the specific steps of which are as follows: (1) Preparation of carboxylated chitosan fibers: Same as step (1) in Example 1.

[0037] (2) Preparation of quaternized chitosan: The same method for preparing quaternized chitosan as in Example 2.

[0038] (3) Preparation of a prepolymer electrolyte complex of quaternized chitosan and carboxymethyl enzymatically hydrolyzed starch: Carboxymethyl hydrolyzed starch was dissolved in deionized water to prepare a 2% starch solution. The pH was adjusted to 6.8 with 1 mol / L NaOH. The quaternized chitosan prepared in step (2) was dissolved in deionized water to prepare a 2% QCS solution. Under stirring conditions, the QCS solution was slowly added dropwise to the starch solution (QCS:starch mass ratio = 4:1). After the addition was complete, stirring was continued for 30 min to obtain a prepolymer electrolyte complex solution.

[0039] (4) Preparation of polyvinyl alcohol mixture: Same as step (2) in Example 1.

[0040] (5) Preparation of chitosan mixed solution: The prepolymer electrolyte complex solution obtained in step (3) is mixed with the carboxylated chitosan fibers prepared in step (1) and stirred until homogeneous to obtain a chitosan mixed solution. The quaternized chitosan in the prepolymer electrolyte complex accounts for 2% of the total mass of the chitosan mixed solution, and the carboxylated chitosan fibers account for 1% of the total mass of the chitosan mixed solution.

[0041] (6) Preparation of crosslinking solution: Add tannic acid (2% of the mass of the polyvinyl alcohol mixture) to the polyvinyl alcohol mixture obtained in step (4) and stir until homogeneous. Then add the chitosan mixture obtained in step (5) (PVA to total solid mass ratio of 1:1) and stir for 30 min to obtain a crosslinking solution.

[0042] (7) Freeze-drying and shaping: Same as step (5) in Example 1. Example 5

[0043] The difference between this embodiment and embodiment 4 is that in step (6), the crosslinking agent is glutaraldehyde, and the amount added is 2% of the mass of the polyvinyl alcohol mixture.

[0044] The remaining steps are the same as in Example 4. Example 6

[0045] The difference between this embodiment and embodiment 4 is that in step (3), the mass ratio of QCS to starch is 3:1.

[0046] The remaining steps are the same as in Example 4. Example 7

[0047] The difference between this embodiment and embodiment 4 is that in step (3), the mass ratio of QCS to starch is 5:1.

[0048] The remaining steps are the same as in Example 4.

[0049] Comparative Example Chitosan (90% degree of deacetylation, molecular weight 150,000) was dissolved in 3% acetic acid solution to prepare a 2% chitosan solution by mass. The solution was poured into a mold and pre-frozen at -30°C for 12 hours. Then, it was freeze-dried at -15°C under vacuum of 10 Pa for 6 hours to obtain pure chitosan sponge.

[0050] Performance Testing and Evaluation 1. Water absorption rate determination: Weigh the sponge sample (1cm×1cm×1cm). Immerse in deionized water, let stand at 37°C until saturated with water, remove and blot off surface moisture with filter paper, then weigh. The water absorption rate is calculated using the following formula:

[0051] 2. Compression strength determination: Using a universal testing machine, the sponge sample (10 mm in diameter and 10 mm in height) was compressed at a rate of 2 mm / min until the strain was 50%, and the compression strength (kPa) was recorded.

[0052] 3. Coagulation Index (BCI) Determination: Place a sponge sample (10 mm in diameter) at the bottom of a test tube, add 0.2 mL of anticoagulated rabbit blood, and then add 0.2 mL of CaCl2 solution (0.025 mol / L) to initiate coagulation. After incubating at 37°C for 5 min, add 25 mL of deionized water and incubate at 37°C for 5 min. Measure the absorbance of the supernatant at 540 nm (A_sample). Use a blank control (A_blank) without sponge. The coagulation index is calculated using the following formula:

[0053] The lower the BCI value, the better the coagulation effect.

[0054] 4. In vitro hemostasis time determination: A rat liver hemorrhage model was used. SD rats (weighing 250-300g) were anesthetized and their abdomens were opened to expose the liver. A standard wound (5mm in diameter, 2mm in depth) was created in the left lobe of the liver. A sponge sample (10mm in diameter) was placed over the wound, and the hemostasis time was recorded every 5 seconds. Medical gauze was used as a control group.

[0055] Table 1 Performance test results of each embodiment and comparative example Example 1 1850 180 22 68 Example 2 2100 195 15 52 Example 3 2200 165 18 58 Example 4 2850 260 10 42 Example 5 2750 245 12 45 Example 6 2650 235 11 44 Example 7 2950 240 10 43 Comparative Example 950 65 45 132 As shown in Table 1, the compressive strength of Examples 1-7 was significantly better than that of the comparative example, indicating that the introduction of carboxylated chitosan fibers significantly enhanced the mechanical properties of the sponge. The compressive strength of Example 4 (260 kPa) was about 300% higher than that of Comparative Example 1 (65 kPa), indicating that the synergistic reinforcing effect of the quaternized chitosan, the prepolymer electrolyte complex of carboxymethyl enzymatically hydrolyzed starch, and the carboxylated fibers was significant.

[0056] The coagulation indices of Examples 1-7 were all superior to those of the comparative examples, indicating that the hemostatic effect of the present invention is significantly better than that of the prior art. Among them, the coagulation index (10%) and hemostasis time (42s) of Example 4 were significantly better than those of the comparative examples (45%, 132s), indicating that the permanent positive charge of quaternized chitosan, the physical adsorption of carboxylated fibers, and the hydrophilic penetration of carboxymethyl enzymatically hydrolyzed starch synergistically enhanced the hemostatic efficiency.

[0057] Compared with Example 3 (tannic acid), Example 1 (glutaraldehyde) showed slightly better water absorption (2200% vs 1850%) and hemolysis rate (1.2% vs 1.8%), but slightly lower compressive strength (165kPa vs 180kPa).

[0058] Data from Example 4 (QCS + carboxymethyl hydrolyzed starch precomplex) show that the introduction of carboxymethyl hydrolyzed starch not only enhances mechanical properties but also further accelerates blood absorption and coagulation processes through strong hydrophilicity. The optimal overall performance was achieved when the QCS:starch ratio was 4:1 (Example 4).

[0059] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing a chitosan hemostatic sponge material, characterized by, Includes the following steps: An emulsifier is added to an aqueous polyvinyl alcohol solution, and the mixture is heated and stirred to obtain a polyvinyl alcohol mixture. Carboxylated chitosan fibers and chitosan were added to an aqueous acetic acid solution to obtain a chitosan mixed solution; A crosslinking agent is added to a polyvinyl alcohol mixture, followed by a chitosan mixture to obtain a crosslinking solution. The crosslinking solution was poured into a film-forming device and freeze-dried under vacuum to obtain chitosan hemostatic sponge material.

2. The production method according to claim 1, characterized by, The polyvinyl alcohol in the aqueous solution has a polyvinyl alcohol mass fraction of 5%-10%; the emulsifier is a nonionic surfactant, accounting for 0.2%-0.5% of the mass of the polyvinyl alcohol mixture.

3. The preparation method according to claim 1, characterized in that, Carboxylated chitosan fibers are prepared by the following steps: acrylic acid is added to anhydrous ethanol, then chitosan fibers are added, and the reaction is carried out at 60-80°C for 24-50 hours; then the mixture is washed until strongly alkaline, then washed until neutral, and finally dried to obtain carboxylated chitosan fibers.

4. The preparation method according to claim 1, characterized in that, The mass fraction of the acetic acid aqueous solution is 2-5%, the mass of chitosan accounts for 1-3% of the total mass of the chitosan mixed solution, and the mass of carboxylated chitosan fibers accounts for 0.5-2% of the total mass of the chitosan mixed solution.

5. The preparation method according to claim 1, characterized in that, The crosslinking agent is glutaraldehyde or tannic acid, accounting for 1-3% of the mass of the polyvinyl alcohol mixture.

6. The preparation method according to claim 1, characterized in that, The steps of freeze-vacuum drying include: pre-freezing: pre-freezing the crosslinking solution at -40 to -20°C for 0.5-24 hours, and then freezing it at a vacuum of 1-20 Pa and -20°C to -5°C for 2-10 hours.

7. The preparation method according to claim 1, characterized in that, Chitosan is either quaternized chitosan or a complex of quaternized chitosan and carboxymethyl enzymatically hydrolyzed starch prepolymer electrolyte.

8. The preparation method according to claim 7, characterized in that, Quaternized chitosan is obtained through the following steps: chitosan is dissolved in acetic acid solution, then 2,3-epoxypropyltrimethylammonium chloride is added, and the mixture is reacted at 40-90°C for 12-24 hours. After purification, the chitosan is freeze-dried to obtain quaternized chitosan.

9. The preparation method according to claim 1, characterized in that, The quaternized chitosan and carboxymethyl hydrolyzed starch prepolymer electrolyte complex is obtained through the following steps: carboxymethyl hydrolyzed starch is dissolved in deionized water to obtain a starch solution, wherein the concentration of carboxymethyl hydrolyzed starch is 1-3%; then the pH is adjusted to 6.5-7.0 with NaOH; quaternized chitosan is dissolved in water and slowly added dropwise to the starch solution while stirring, wherein the mass of carboxymethyl hydrolyzed starch accounts for 2-8% of the mass of quaternized chitosan.

10. A chitosan hemostatic sponge material, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.

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