Highly-crimped superfine fiber material, preparation thereof and application of highly-crimped superfine fiber material in hemostatic material

Abstract

The invention relates to the technical field of biological materials, and provides a highly-curled superfine fiber material, preparation thereof and application of the highly-curled superfine fiber material in hemostatic materials, the curled superfine fiber material is prepared by adopting a solution blowing spinning technology, and the curled superfine fiber material comprises curled nanofibers with the diameter smaller than 1 micron and the average bending angle larger than or equal to 220 degrees. The in-situ highly-crimped superfine fiber is prepared by optimizing a turbulent flow field, the high specific surface area and the enhanced porosity of the in-situ highly-crimped superfine fiber ensure the rapid hemostatic effect, and the in-situ highly-crimped superfine fiber can adapt to complicated clinical environments such as high-pressure arterial bleeding, irregular wound surfaces and deep wounds.

Description

Technical Field

[0001] The present invention relates to the technical field of biomaterials, in particular to a highly curled ultrafine fiber material, a preparation method thereof, and an application thereof in hemostatic materials. Background Art

[0002] In scenarios such as battlefield rescue, emergency medical treatment, and complex surgery, a large amount of hemostatic materials are required. Conventional hemostatic technologies include materials such as gauze, powder, hydrogel, sponge, and microfiber, each with its own characteristics. Among them, microfibers, with their high specific surface area and biomimetic properties, can provide rapid coagulation and infection prevention and control effects. However, the structure of the current mainstream microfibers is relatively simple. Although research on microfibers with different curling morphologies has been reported, the application performance of existing curling morphologies of microfibers as raw materials for hemostatic materials still needs to be improved. Summary of the Invention

[0003] The present invention provides a highly curled ultrafine fiber material, its preparation and application in hemostatic materials. Through specific spinning equipment and optimized spinning process parameters, the preparation of curled ultrafine fibers with a diameter less than 1 μm and an average bending angle of the curled ultrafine fibers greater than or equal to 220° is achieved.

[0004] In a first aspect, the present invention provides a curled ultrafine fiber material prepared by solution blowing technology, comprising: curled nanofibers with an average fiber diameter of less than 1 μm and an average bending angle greater than or equal to 220°.

[0005] Preferably, the fiber diameter is 10 nm to 800 nm.

[0006] According to the curled microfiber material provided by the present invention, the curled microfibers with a bending angle greater than or equal to 250° in the curled microfiber material account for more than 50% of the total number of fibers, preferably more than 60%; And / or, the average fiber diameter of the curled nanofibers is 10 to 800 nm, preferably 50 to 600 nm, more preferably 100 to 550 nm, and more preferably 200 to 500 nm.

[0007] According to the curled ultrafine fiber material provided by the present invention, the porosity of the curled ultrafine fiber material is 90% to 99.999%, preferably 90% to 99%, further preferably 90% to 95%, and more preferably 90% to 92%; And / or, the volume density of the curled ultrafine fiber material is 10~200 mg / cm³, preferably 10~100 mg / cm³, further preferably 10~50 mg / cm³, and more preferably 10~20 mg / cm³.

[0008] The composition of the curled ultrafine fiber material of the present invention is not particularly limited and may include one or a combination of two or more of organic polymers, inorganic non-metals, and metals.

[0009] According to the curled microfiber material provided by the present invention, the curled microfiber The matrix is ​​a soluble polymer; Preferably, the soluble polymer is one or a combination of two or more of a degradable polymer, PMMA, PVB, and PU; the degradable polymer may preferably be one or a combination of two or more of PCL, PLA, and PLGA; and / or, the curled nanofibers optionally include a functional component; The functional component is preferably one or a combination of two or more selected from the group consisting of hydrophilic modified polymers, natural polymers, coagulant proteins, sodium alginate, and inorganic particles; the hydrophilic modified polymer is preferably one or a combination of two or more selected from the group consisting of polyethylene oxide and polyethylene glycol; the natural polymer is preferably one or a combination of two or more selected from the group consisting of chitosan, collagen, and cellulose, and more preferably chitosan; the inorganic particles are preferably inorganic nanoparticles, and more preferably one or a combination of two or more selected from the group consisting of silicon dioxide nanoparticles, zinc oxide nanoparticles, and silver nanoparticles, and even more preferably silver sulfadiazine powder; Further preferably, the content of the functional component is more than 30% of the mass of the polymer, more preferably more than 50%, more than 100%, more than 200%, more than 300%; and / or, the content of the hydrophilic modified polymer is more than 30% of the mass of the curled nanofiber, more preferably more than 35%, more than 40%, more than 45%.

[0010] When the functional component is chitosan, it can adsorb negatively charged plasma proteins through electrostatic interactions and form hydrogen bonds with fibrin. The amino groups (-NH2) on chitosan can covalently crosslink with aldehyde or carboxyl groups in the blood (e.g., Schiff base reactions or amide bond formation), further stabilizing the hemogel structure, allowing it to seal wounds like a bandage and promote tissue repair.

[0011] When the functional component is selected from sodium alginate, it can react with calcium ions (Ca 2+ ) undergo ionic crosslinking to form a stable gel network. The gel network of sodium alginate works synergistically with the electrostatic adsorption and covalent crosslinking of chitosan to improve the stability of the hemostatic material and enhance the wound repair effect.

[0012] When the functional component is selected from a mixture of chitosan and sodium alginate, chitosan and sodium alginate can work synergistically to form a stable blood gel structure.

[0013] Preferably, the particle size distribution of the inorganic particles is 10-500 nm. Inorganic particles within this range can be evenly distributed in the curled ultrafine fibers of the present invention without affecting the integrity of the fiber structure.

[0014] The hydrophilic modified polymer can enhance the fiber's affinity for blood, improve wound adhesion, and promote the stable formation of blood gels, thereby further enhancing hemostasis and tissue repair performance. Furthermore, the addition of polyethylene oxide and polyethylene glycol to the spinning solution increases the solution's viscosity and provides the potential for modification.

[0015] The functional components of the curled microfiber material of this invention can adapt to different tissue environments, ensuring an optimal balance between hemostatic efficacy and flexibility. The functions of the inorganic particles can be customized, and the coagulant factor, antibacterial component, or growth factor can be adjusted according to application requirements to achieve a multifunctional hemostatic material.

[0016] The high porosity and three-dimensional, tortuous structure of the curled microfibers of this invention significantly increase their specific surface area, providing more adsorption and embedding sites for inorganic particles and improving their loading capacity. The interlaced network formed by the curled structure allows for a more uniform dispersion of inorganic particles within the fiber matrix, preventing agglomeration and improving particle stability and controllable release within the fiber. The particles can provide functions such as coagulant promotion, antibacterial properties, and drug release, and can even impart medical imaging capabilities such as fluorescent labeling and contrast enhancement to expand clinical applications.

[0017] As an illustration, when the surface of the curled microfibers contains one or a combination of two or more of the following: procoagulant proteins, nano-silica, and chitosan as functional components, this functional group can adsorb platelets, inducing their activation and release of coagulation factors, accelerating the coagulation cascade. The adsorption of plasma proteins on the fiber surface is enhanced, causing the protein molecules to cross-link to form a high-strength gel, ensuring that the blood is effectively locked into the curled microfiber network. The blood is captured within the fiber skeleton and stably coagulated. The blood gel adheres tightly to the wound, achieving efficient hemostasis in a short period of time and promoting wound healing through cross-linking.

[0018] Preferably, the particle size distribution of the inorganic particles is 100 nm to 10 μm.

[0019] In a second aspect, the present invention also provides a method for preparing the above-mentioned curled ultrafine fiber material, comprising: using a spinning solution as a raw material and adopting a solution blowing technology to prepare the material; the spinning equipment used in the solution blowing technology includes a spray gun and a liquid supply device; The spray gun comprises: An air supply device, used for forming an airflow, wherein the airflow is a horizontal flow; A cavity, comprising: a first air passage, communicating with the air supply device; a second airway, communicating with the first airway; a third airway, communicating with the second airway; a sheet-like object having at least two through holes and disposed in the cavity; The first air channel is used to form turbulence, the sheet is used to enhance the intensity and uniformity of the turbulence, the cross section of the second air channel gradually narrows along the airflow direction to converge the turbulence; the third air channel is used to guide the converged turbulent flow to be ejected; The liquid supply direction of the liquid supply device intersects with the direction of the airflow sprayed from the spray gun; preferably, the intersection of the extension line of the liquid supply direction of the liquid supply device and the extension line of the direction of the airflow sprayed from the spray gun is located 0.1~5cm in front of the outlet end of the spray gun; further preferably, the liquid outlet of the liquid supply device is located on the central axis of the third air duct, and the distance d from the outlet of the third air duct is 0.1~5cm, and further preferably, the distance d is 0.1~2cm, 0.15~1.5cm, or 0.2~1cm.

[0020] According to the preparation method provided by the present invention, the airflow formed by the spray gun is simulated under a pressure difference of one atmosphere, and the airflow velocity at 80 cm from the outlet of the third air channel is greater than or equal to 190 m / s; the turbulent kinetic energy at 45 mm from the outlet of the third air channel is greater than or equal to 1500 kg / (m×s 2 ).

[0021] First, the spinning solution ejected from the liquid outlet is acted upon by the airflow ejected from the spray gun to form a preliminary liquid jet. Due to the large difference in velocity between the gas and the solution, shear instability occurs at the jet interface, causing the liquid jet to split and thin, and form tiny droplets or filaments. Subsequently, between the nozzle and the surrounding environment, the kinetic energy of the airflow is converted into an intense local turbulent field due to the violent disturbance caused by the ejected airflow passing through the porous obstacle structure. Turbulent characteristics include large velocity gradients, strong vortex structures, and multi-scale energy distribution, forming a non-uniform, pulsating flow field environment.

[0022] After the airflow passes through the outlet, the initial flow is primarily affected by jet inertia and shear disturbances, resulting in an unstable flow field and drastically changing velocity distribution. Turbulent kinetic energy is primarily generated and rapidly develops by the high-speed shear near the nozzle. As the airflow propagates axially, part of the initial kinetic energy is converted into turbulent pulsating energy. The airflow undergoes thorough mixing, the turbulent kinetic energy distribution gradually stabilizes, and the flow field enters the turbulent self-similarity zone. At this point, the local airflow velocity and its pulsation amplitude are closely related to the turbulent kinetic energy. The greater the velocity and the stronger the pulsation, the higher the corresponding turbulent kinetic energy. Because the decay of turbulent kinetic energy in space is continuous and predictable, the airflow velocity and pulsation characteristics at a certain distance from the outlet (e.g., 80 cm) can comprehensively reflect the overall turbulent kinetic energy output level of the device. Simply put, the higher the airflow velocity and the more drastic the fluctuations, the greater the turbulent kinetic energy output of the system.

[0023] It was also found in the experiment that the airflow field formed outside the outlet of the spray gun of the present invention includes a turbulent section, wherein the length of the turbulent section is more than 90 mm. The liquid outlet is set at the above-mentioned position, so that the spinning jet formed by the spinning solution ejected from the liquid outlet can be fully acted upon by the strong turbulent section. Under the action of turbulence, the liquid filaments are subjected to the combined action of multi-directional shear force, tensile force and disturbance torque, so that the filaments are continuously stretched, folded and whipped. Especially in the high vortex area, the fiber locally produces periodic bending, twisting and circuitousness, thereby inducing a highly curled structure. In this process, the fiber surface simultaneously undergoes rapid solvent volatilization, and the liquid jet gradually solidifies into a solid, curled ultrafine fiber.

[0024] According to the preparation method provided by the present invention, the sheet-like object includes: a circular gasket provided with more than 37 through holes, and further preferably, protrusions and / or grooves are formed on the inner walls of the through holes along the airflow direction.

[0025] According to the preparation method provided by the present invention, the radial direction of the circular gasket is perpendicular to the airflow direction of the first airway, and the axial direction of the through hole is parallel to the airflow direction of the first airway.

[0026] According to the preparation method provided by the present invention, the thickness of the circular gasket is in the range of 2 to 5 mm, and the distance between two adjacent through holes is in the range of 0.1 to 3 mm.

[0027] According to the preparation method provided by the present invention, the air flow velocity V is greater than 18 m / s when measured along the axial extension of the central axis of the third air channel and 6 mm away from the central axis on a cross section at a position 75 mm away from the end face of the third air channel.

[0028] Because the high-speed jet airflow exhibits a radially attenuated distribution, the airflow velocity is highest in the center, and then decreases rapidly with increasing radial distance. Experiments in preparing fiber materials found that the airflow velocity is highest at the center axis of the nozzle, while the velocity decreases significantly at a position 6 mm off-center, where the velocity is significantly attenuated. For example, in the present invention, an airflow velocity V of 18 m / s or higher at this location helps produce fiber materials with a higher degree of curl.

[0029] Within a certain range, the longer the receiving distance, the smaller the fiber diameter. However, if the receiving distance is too long, it will easily lead to low fiber yield and inability to achieve effective collection. Therefore, preferably, the distance L between the liquid outlet of the liquid supply device and the receiving device is 25~35cm.

[0030] According to the preparation method provided by the present invention, the sheet-like object is provided in the first airway, the second airway, or the connection between the first airway and the second airway.

[0031] The preparation method provided by the present invention further includes: an integrated tubular structure comprising: A cylindrical tubular structure, wherein the first airway formed inside is a circular tubular channel; A truncated cone-shaped tubular structure is an integral structure with the cylindrical tubular structure, and the second air channel and the third air channel are sequentially formed inside the truncated cone-shaped tubular structure along the airflow direction; A trapezoidal mounting block has one end connected to the end surface of the cylindrical tubular structure and the other end inserted into the interior of the cylindrical tubular structure and presses the sheet into the cavity.

[0032] According to the preparation method provided by the present invention, the inner diameter of the cylindrical tubular structure and the inner diameter of the bottom surface of the truncated cone-shaped tubular structure are the same, and the value range is 1~10 cm; the height of the cylindrical tubular structure is in the range of 5~25 cm, preferably 5~20 cm, 5~15 cm, 6~12 cm, 6~10 cm; the height of the truncated cone-shaped tubular structure is in the range of 1~5 cm, preferably 1~4 cm, 1~3 cm, 1~2 cm; the inner diameter of the top surface of the truncated cone-shaped tubular structure is in the range of 3~10 mm, preferably 3~8 mm, 3~6 mm, 3~5 mm, 4 mm.

[0033] Preferably, the spray gun further comprises a holding device fixedly connected to the cavity.

[0034] Preferably, the spinning equipment further comprises: a mounting plate formed with a mounting groove, the mounting groove being used to clamp the spray gun, and the liquid supply device is assembled on the mounting plate.

[0035] In a third aspect, the present invention further provides a hemostatic material, comprising the curled ultrafine fiber material as described above, or the curled ultrafine fiber material prepared by the preparation method as described above.

[0036] The fine structure and capillary effect of ultrafine fibers promote the rapid penetration of blood into the fiber pores, accelerating platelet aggregation and the action of coagulation factors. At the same time, the high curl and high fluffiness of ultrafine fibers increase the storage capacity of blood in the material, forming a preliminary hemostatic barrier.

[0037] Compared with traditional hemostatic materials, its highly curled fiber structure increases the porosity and contact density, enhances the interaction between blood and ultrafine fibers, improves the ability to capture coagulation factors, and enhances the adsorption of plasma proteins on the fiber surface, causing protein molecules to cross-link to form a high-strength gel, accelerating the blood coagulation process.

[0038] Preferably, the tensile strength of the hemostatic material is 0.01-10 MPa, and the elongation at break of the hemostatic material is 10%-800%, so as to ensure that it has good biocompatibility in different application environments.

[0039] The appropriate viscosity coefficient can ensure that the hemostatic material will not fall off easily due to mechanical disturbance, while avoiding excessive adhesion that affects replacement or secondary treatment.

[0040] Appropriate peeling force can ensure that the hemostatic material can be stably attached to the wound surface without tearing the tissue or causing secondary damage due to excessive adhesion.

[0041] According to the hemostatic material provided by the present invention, the 90° peeling force between the curled microfiber material and the liver tissue is 1-5 kPa.

[0042] The curled ultrafine fiber material provided by the present invention further includes: blood captured by the curled ultrafine fiber material, and the blood and the curled ultrafine fibers are cross-linked to form a three-dimensional network.

[0043] The three-dimensional network as a whole in the present invention is also called blood gel, which includes the curled ultrafine fiber material and a gel formed by cross-linking of plasma proteins captured in the curled ultrafine fiber material through the action of coagulation factors.

[0044] The curled microfiber material of the present invention can capture blood in 5 seconds to 2 minutes due to its highly curled structural characteristics. The blood coagulates in 5 to 10 minutes to obtain the blood gel, thereby ensuring rapid hemostasis, adapting to different types of bleeding environments, and taking into account gel stability and tissue healing.

[0045] According to the hemostatic material provided by the present invention, the mass of blood captured by the curled ultrafine fiber material is more than 600% of the mass of the curled ultrafine fibers.

[0046] The present invention provides a highly curled microfiber material, its preparation, and its application in hemostatic materials. Through specific spinning equipment and optimized spinning process parameters, it achieves the production of curled microfibers with a diameter less than 1 μm and an average bending angle of greater than or equal to 220°. Furthermore, this highly curled microfiber material exhibits unique application advantages in hemostatic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction is given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0048] Figure 1 It is a schematic diagram of the internal structure of the spray gun provided by the present invention.

[0049] Figure 2 It is a cross-sectional view of the cavity and sheet provided by the present invention.

[0050] Figure 3 It is a structural schematic diagram of the sheet provided by the present invention.

[0051] Figure 4 It is a schematic diagram of an optional structure of a through hole in a sheet provided by the present invention.

[0052] Figure 5 It is a schematic diagram of an optional structure of a through hole in a sheet provided by the present invention.

[0053] Figure 6 It is a schematic diagram of an optional structure of a through hole in a sheet provided by the present invention.

[0054] Figure 7 It is a schematic structural diagram of the spinning device provided in Equipment Example 1 of the present invention.

[0055] Figure 8 This is an SEM image of the highly curled ultrafine fiber material of Example 3 provided by the present invention.

[0056] Figure 9 This is a test result diagram of Test Example 2 provided by the present invention.

[0057] Figure 10 This is a physical picture of Test Example 3 provided by the present invention.

[0058] Figure 11 This is the SEM image of Test Example 3 provided by the present invention.

[0059] Figure 12 This is the element distribution diagram of Test Example 3 provided by the present invention.

[0060] Figure 13 Schematic diagram of the red blood cells of Test Example 3 provided by the present invention.

[0061] Figure 14 This is a test result diagram of Test Example 4 provided by the present invention.

[0062] Figure 15 This is a physical picture of Test Example 5 provided by the present invention.

[0063] Figure 16 This is a real picture of the rat liver after seven days in Test Example 5 provided by the present invention.

[0064] Figure 17 This is an enlarged physical picture of the rat liver after seven days in Test Example 5 provided by the present invention.

[0065] Figure 18 3 is a stress-strain curve diagram of Test Example 6 provided by the present invention.

[0066] Figure 19 3 is a stress-strain curve diagram of Test Example 6 provided by the present invention.

[0067] Figure 20 This is a test result diagram of Test Example 7 provided by the present invention.

[0068] Figure 21 This is a test result diagram of Test Example 8 provided by the present invention.

[0069] Figure 22 It is a schematic diagram of measuring the bending angle provided by the present invention. DETAILED DESCRIPTION

[0070] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0071] The following combination Figures 1 to 22 The invention describes a highly curled ultrafine fiber material, its preparation method and its application in hemostatic materials.

[0072] In a specific embodiment of the present invention, a spray gun is first provided. The spray gun includes: an air supply device (not shown in the figure), a cavity, a sheet 201, and the like.

[0073] The air supply device is used to generate a horizontal airflow. The cavity includes a first air channel 101 and a second air channel 102. The first air channel 101 is connected to the air supply device, and the second air channel 102 is connected to the first air channel 101. A flap 201 having at least two through holes 202 is disposed within the cavity. The first air channel 101 is used to generate turbulent flow, and the flap 201 is used to enhance the turbulent flow's intensity and uniformity. The cross-section of the second air channel 102 gradually narrows along the airflow direction, converging the turbulent flow.

[0074] Specifically, the air supply device can use a compressed air pump to generate high-pressure airflow (horizontal flow). The air outlet of the compressed air pump is connected to the first air channel 101 of the cavity. After the high-pressure airflow enters the first air channel 101, it becomes turbulent or the intensity of the turbulence is increased. The disturbance of the airflow can be increased by changing the extension direction or inner diameter of the first air channel 101. It can also be converted into turbulent flow by increasing the air pump suction power and the air flow blowing speed.

[0075] Specifically, the second air channel 102 is connected to the outlet of the first air channel 101. The turbulent flow after passing through the first air channel 101 flows into the second air channel 102. After passing through the sheet 201, the turbulent flow is disturbed by the porous array, further improving the uniformity and turbulence intensity, forming a multi-jet homogeneous turbulent flow. The inner diameter of the second air channel 102 gradually narrows along the direction of airflow. By reducing the diameter, the turbulent flow is converged, resulting in higher turbulent kinetic energy.

[0076] Specifically, a sheet 201 is disposed within the cavity. Depending on the specific situation, it can be disposed in the first air channel 101, the second air channel 102, or the connection between the first air channel 101 and the second air channel 102. The sheet 201 is formed with at least two through holes 202. After the turbulent flow passes through the through holes 202, the turbulent flow intensity and uniformity are further increased.

[0077] Preferably, the sheet 201 may be designed with a plurality of through holes 202 to form a porous structure. After the airflow passes through the porous structure, a multi-jet homogeneous turbulent flow is formed.

[0078] Optionally, depending on the specific usage scenario of the handheld spray gun, the gas supply device can be filled with different types of gases, such as nitrogen (which can prevent thrombosis), carbon dioxide (which can perform nerve repair) or argon.

[0079] Optionally, the sheet 201 can be of any shape and size, such as circular disks of different sizes, square disks, etc.; the through holes 202 on the sheet 201 can be of any shape, such as square holes, polygonal holes, etc.; the through holes 202 on the sheet 201 can be set with different row and column spacings.

[0080] The spray gun provided by the present invention is applied to solution blow spinning technology and is generally used in conjunction with a needle tube filled with a precursor solution. The liquid outlet of the needle tube is located in the airflow output by the handheld spray gun, so that the fibers produced are curled ultrafine fibers. The specific usage is as follows: S1, turn on the compressed air pump to provide high-speed airflow; S2, the airflow passes through the inside of the handheld spray gun, and then passes through the first air channel 101, the second air channel 102, the sheet 201 and other structures in sequence, forming a convergent turbulent flow with high turbulent kinetic energy; S3. A needle is used to squeeze the precursor solution and position it at the liquid outlet of the needle tube. A high-speed airflow blows the precursor solution out of the liquid outlet, forming a straight jet. After the jet enters the turbulent field formed by the handheld spray gun, it interacts with small vortices in the turbulent field, causing the small vortices to bend the straight jet. The combined action of multiple vortices in the turbulent field causes the jet to whip violently, thereby producing curly microfibers. The liquid outlet can be a hole at the end of the needle tube, through which the high-speed airflow blows the precursor solution.

[0081] In addition, if the sheet 201 is designed with a porous structure, the multi-jet turbulence formed therein causes the solution to whip violently, which will accelerate the volatilization of the solvent and improve the efficiency of preparing the curled ultrafine fibers, and can be used for large-scale preparation of curled ultrafine fibers.

[0082] In addition, the spray gun provided by the present invention is a handheld device that can be independent of the needle tube and has a holding device for the handheld device, which is convenient for processing and use.

[0083] In some embodiments of the present invention, a sheet 201 having a through-hole 202 is used inside the spray gun, and the first air channel 101 and the second air channel 102 are used to form a convergent turbulent flow, thereby significantly increasing the turbulent kinetic energy of the induced turbulent flow field, dense homogeneous vortices, and violent disturbances at the gas-liquid interface. This enables high-throughput formation of ultrafine fiber membranes accompanied by airflow pressure, which has the following advantages: 1) Through the structural design of the through-hole 202 of the sheet 201, the preparation of curly ultrafine fibers with lower diameter, higher curvature, porosity and lower average pore size can be achieved, thereby increasing the contact point density per unit volume of the fiber, exerting the capillary effect of the ultrafine fiber skeleton, enhancing its advantages in fields requiring high-level in-situ preparation such as hemostasis, adsorption, and warmth preservation, and effectively reducing the conduction rate of various media.

[0084] 2) Due to the handheld spray gun structure design, the portability of the equipment is greatly improved. It can be independent of needles or large equipment and can be prepared in various outdoor environments, solving the problem of conventional technology having high equipment requirements.

[0085] It can be seen that the spray gun provided by the present invention utilizes the principle of convergent turbulent field to produce curled ultrafine fiber materials with high porosity, low average pore size and high bending angle through convergent turbulent spinning. The process is simple, universal, low cost and high efficiency, and it has good industrial prospects and value.

[0086] In some embodiments of the present invention, a spray gun includes an air supply device, a cavity, and a flap 201. The air supply device is used to generate a horizontal airflow. The cavity includes a first air channel 101 and a second air channel 102; the first air channel 101 is connected to the air supply device, and the second air channel 102 is connected to the first air channel 101. The flap 201 has at least two through holes 202 and is disposed within the cavity. The first air channel 101 is used to generate turbulent flow, and the flap 201 is used to enhance the intensity and uniformity of the turbulent flow. The cross-section of the second air channel 102 gradually narrows along the airflow direction to converge the turbulent flow. The spray gun provided by the present invention, through the first air channel 101, the second air channel 102 in the cavity and the through hole 202 in the sheet 201, changes the air flow from the laminar flow in the air supply device to the turbulent flow with higher turbulent kinetic energy. It can be applied to solution blowing technology, and can achieve the preparation of curly ultrafine fibers with lower diameter, higher curl, porosity and lower average pore size, thereby increasing the density of contact points per unit volume of the fiber, giving play to the capillary effect of the curly ultrafine fiber skeleton, enhancing its advantages in high-level fields such as hemostasis, adsorption, and warmth preservation that require in-situ preparation, and effectively reducing multiple conduction rates; adopting a handheld spray gun structure design, the portability of the equipment is greatly improved, and it can be independent of a needle or large equipment, and can be prepared in various outdoor environments, solving the problem of high equipment requirements of conventional technology. In addition, the ultrafine fibers with a highly curled structure can increase the loading sites, load stability and load uniformity of drugs, functional particles, etc., thereby improving material properties.

[0087] In some embodiments of the present invention, the cavity further includes: a third air channel 103, which is connected to the second air channel 102 and is used to guide the converged turbulent jet. In this embodiment, the cavity further includes the third air channel 103. The first air channel 101, the second air channel 102, and the third air channel 103 are sequentially formed in the cavity along the direction of airflow movement, and their functions are: The first air channel 101 is used to transform laminar flow into turbulent flow; the second air channel 102 is used to converge the turbulent flow, giving it higher turbulent kinetic energy; and the third air channel 103 is used to guide the turbulent flow out. The inner diameter of the third air channel 103 is the same as the inner diameter of the outlet of the second air channel 102, and it has a certain length, guiding the turbulent flow out of the third air channel 103. These three air channels are connected in sequence, forming a nozzle structure at the outlet. That is, the outer end surface of the third air channel 103 forms a nozzle structure.

[0088] In some embodiments of the present invention, the sheet 201 is provided in the first air channel 101, the second air channel 102, or the connection between the first air channel 101 and the second air channel 102. The present invention also protects various curly microfiber materials prepared by the above-mentioned method for preparing curly microfibers using a handheld spray gun.

[0089] In some embodiments of the present invention, the sheet 201 is located in the first airway 101, preferably in the middle or tail of the first airway 101. After the airflow forms turbulence in the first airway 101, the turbulence intensity of the turbulence is further enhanced through the through holes 202 of the sheet 201.

[0090] In some embodiments of the present invention, the sheet 201 is located in the second air channel 102, preferably in the middle or tail of the second air channel 102. The airflow forms turbulence through the first air channel 101, and after the second airflow converges, it passes through the through hole 202 of the sheet 201, further enhancing the turbulence intensity of the turbulence.

[0091] In some embodiments of the present invention, the sheet 201 is located at the connection between the first air duct 101 and the second air duct 102, that is, the junction between the two. After the airflow forms turbulence in the first air duct 101, it passes through the through hole 202 of the sheet 201, further enhancing the turbulence intensity and uniformity of the turbulence. Finally, the turbulence is converged by the second airflow.

[0092] It has been found through experiments that, in the above three embodiments, installing the sheet 201 at the connection between the first air channel 101 and the second air channel 102 can generate greater turbulent kinetic energy.

[0093] In some embodiments of the present invention, the spray gun further comprises: an integrated tubular structure and a trapezoidal mounting block 303. The integrated tubular structure comprises: a cylindrical tubular structure 301 and a truncated cone-shaped tubular structure 302. The first air channel 101 formed inside the cylindrical tubular structure 301 is a circular tubular channel; the truncated cone-shaped tubular structure 302 is an integrated structure with the cylindrical tubular structure 301, and a second air channel 102 and a third air channel 103 are sequentially formed inside the truncated cone-shaped tubular structure 302 along the direction of air flow. One end of the trapezoidal mounting block 303 is connected to the end face of the cylindrical tubular structure 301, and the other end is inserted into the interior of the cylindrical tubular structure 301, and presses the sheet 201 into the cavity.

[0094] In some embodiments of the present invention, the cavity has an integrated tubular structure, wherein the integrated tubular structure is an integrated structure of a cylindrical tubular structure 301 and a truncated cone-shaped tubular structure 302. A first airway 101 having a constant inner diameter is formed inside the cylindrical tubular structure 301, and a second airway 102 narrowing along the airflow direction and a third airway 103 having a constant inner diameter are formed inside the truncated cone-shaped tubular structure 302.

[0095] In some embodiments of the present invention, the trapezoidal mounting block 303 is a straight tube structure, the outer diameter of which is adapted to the inner diameter of the first air channel 101 and can be inserted into the first air channel 101. After the trapezoidal mounting block 303 is inserted into the first air channel 101, the sheet 201 is pushed into the designated position, and the trapezoidal mounting block 303 is fixed to the cylindrical tubular structure 301, thereby limiting the position of the sheet 201. After the trapezoidal mounting block 303 is inserted, the inner diameter of the trapezoidal mounting block 303 serves as the first air channel 101 through which the airflow passes. Preferably, the trapezoidal mounting block 303 has a trapezoidal groove for clamping and fixing with the end face of the truncated cone-shaped tubular structure 302. The position of the trapezoidal groove should meet the requirements of fixing with the end of the cylindrical tubular structure 301 and inserting the sheet 201 into the cavity to a designated depth.

[0096] In some embodiments of the present invention, the inner diameter of the cylindrical tubular structure 301 and the inner diameter of the bottom surface of the truncated cone-shaped tubular structure 302 are the same, and the value range is 1~10 cm; the height of the cylindrical tubular structure 301 is in the range of 5~25 cm, preferably 5~20 cm, 5~15 cm, 6~12 cm, 6~10 cm; the height of the truncated cone-shaped tubular structure 302 is in the range of 1~5 cm, preferably 1~4 cm, 1~3 cm, 1~2 cm; the inner diameter of the top surface of the truncated cone-shaped tubular structure 302 is in the range of 3~10 mm, preferably 3~8 mm, 3~6 mm, 3~5 mm, 4 mm.

[0097] In some embodiments of the present invention, the sheet 201 includes: a circular gasket. The circular gasket is provided with a plurality of through holes 202, and protrusions and / or grooves are formed on the inner wall of the through hole 202 along the airflow direction. The sheet 201 in this embodiment adopts a circular gasket, on which a plurality of through holes 202 are evenly distributed. The size of the circular gasket is adapted to the inner diameter of the cavity to ensure that it can be placed in the cavity. It can be understood that the circular gasket has a certain thickness, the circular through hole 202 has a certain length, and the spacing and aperture of the circular through hole 202 are determined according to actual conditions. Protrusions and / or grooves are formed on the inner wall surface of the through hole 202, and the protrusions and / or grooves can be arranged in the length direction and circumferential direction of the through hole 202. Preferably, the protrusion and groove structure can be a trapezoidal / rectangular protrusion and a trapezoidal / rectangular groove, or a stepped protrusion and a stepped groove, or an arc-shaped protrusion and an arc-shaped groove.

[0098] like Figures 4-6 In the structure shown, for the sake of convenience, different shapes of protrusions and / or grooves are arranged in the same through hole 202. However, in general, for the sake of convenience in processing, only protrusions and / or grooves of the same shape are arranged in the same through hole 202. Figure 7 In the structure shown, a groove is formed on the inner wall of the through hole 202; Figure 8 In the structure shown, a protrusion is formed on the inner wall of the through hole 202; Figure 9 In the structure shown, protrusions and grooves are formed on the inner wall of the through hole 202 .

[0099] In the groove and / or protrusion structure formed inside the above-mentioned through hole 202, the protrusion and / or groove structure has the function of guiding and pulling the airflow. Under the interference of the microstructure of the protrusion and / or groove, the airflow will be disturbed by small obstacles, further increasing the turbulence intensity and chaos, and improving the isotropy of the vortex.

[0100] In some embodiments of the present invention, the radial direction of the circular gasket is perpendicular to the airflow direction of the first air channel 101 , and the axial direction of the through hole 202 is parallel to the airflow direction of the first air channel 101 .

[0101] In some embodiments of the present invention, the thickness of the circular gasket ranges from 2 to 5 mm, and the spacing between adjacent through-holes ranges from 0.1 to 3 mm. The through-holes may be staggered. Preferably, the through-holes may be round, square, or star-shaped. If round, a diameter of 1 mm is preferred, and the optimal spacing between rows and columns of the holes is 0.1 to 3 mm.

[0102] In some embodiments of the present invention, the spray gun further comprises a gripping device fixedly connected to the cavity. Specifically, the gripping device can be a handle, enabling hand-held use. Preferably, the gripping device is fixedly connected to the cylindrical tubular structure 301 of the integrated tubular structure. Preferably, the gripping device can be a handle.

[0103] In some embodiments of the present invention, a liquid supply device 400 is provided outside the spray gun.

[0104] The liquid supply direction of the liquid supply device 400 intersects with the gas supply direction of the spray gun. The liquid supply device 400 can be a needle tube structure, which is filled with the precursor solution and can be sprayed out from the end of the needle tube.

[0105] Specifically, the spray gun can be installed together with the liquid supply device 400, and by adjusting the angle between the two, the liquid supply direction of the liquid supply device 400 intersects with the gas supply direction of the spray gun.

[0106] Specifically, the liquid supply port of the liquid supply device 400 is a needle-free design, achieving "needle-free" (i.e., the liquid supply port of the syringe is a needle-free structure). The "needle-free" design achieves needle-free high throughput. This expands the scope of use and improves safety.

[0107] In some embodiments of the present invention, the extended line of the liquid supply direction of the liquid supply device 400 intersects 0.1 to 5 cm in front of the extended line of the air supply direction of the spray gun. Specifically, the outlet end of the liquid supply device 400 is located on the central axis 0.1 to 5 cm in front of the outlet end of the handheld spray gun, ensuring high-speed turbulent flow acting on the precursor solution.

[0108] In some embodiments of the present invention, the spray gun further includes: a mounting plate 500. The mounting plate 500 is formed with a mounting groove, which is used to clamp the spray gun, and the liquid supply device 400 is assembled on the mounting plate 500. Specifically, the mounting plate 500 is a symmetrical structure, and the mounting groove is a semicircular groove. The two mounting plates 500 are respectively clamped on the outside of the cylindrical structure of the handheld spray gun, and their upper parts are fixed to the liquid supply device 400 by another clamping plate 600. Optionally, the clamping plate 600 is similar in structure to the above-mentioned mounting plate 500, with one end connected to the mounting plate 500 and the other end forming a clamping groove for clamping the liquid supply device 400. Through the above-mentioned structure of this embodiment, the liquid supply device 400 and the handheld spray gun can be assembled together, which has the advantages of simple structure and easy disassembly and assembly.

[0109] If no specific techniques or conditions are specified in the examples, the experiments were carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0110] The spinning equipment used in the following embodiments of the present invention is as follows: Equipment Example 1 A spinning device includes a handheld spray gun and a liquid supply device 400.

[0111] The handheld spray gun includes a compressed air pump (not shown in the figure), a cavity and a sheet 201 .

[0112] A compressed air pump is used to form the airflow, and the airflow is a horizontal flow.

[0113] The sheet 201 is a disc with a diameter of 20.0 mm and a thickness of 5 mm. Along the thickness direction, the disc has 37 through holes 202 with circular cross-sections. The diameter of the through holes 202 is 1.0 mm, and the spacing between adjacent through holes 202 is 0.5 mm. The centers of the projection surfaces of all through holes 202 are connected, and the center of gravity of the formed figure is located at the center of the disc.

[0114] The integrated tubular structure includes a cylindrical tubular structure 301, a truncated cone-shaped tubular structure 302, and a trapezoidal mounting block 303. The interior of the cylindrical tubular structure 301 is a first cylindrical cavity with a length of 63 mm. The interior of the truncated cone-shaped tubular structure 302 is composed of a truncated cone-shaped cavity and a second cylindrical cavity. The truncated cone-shaped cavity serves as the second air channel 102 and has a length of 11 mm. The second cylindrical cavity serves as the third air channel 103 and has a length of 8 mm. The interior of the trapezoidal mounting block 303 is a cylindrical cavity, which serves as the first air channel 101. The first cylindrical cavity is connected to the large end of the truncated cone-shaped cavity. The cross-sectional diameter of the first cylindrical cavity and the diameter of the large end of the truncated cone-shaped cavity are the same as the outer diameter of the sheet 201, both of which are 20 mm. The small end of the truncated cone-shaped cavity is connected to the second cylindrical cavity. The diameter of the small end of the truncated cone-shaped cavity is the same as the cross-sectional diameter of the second cylindrical cavity, both of which are 4 mm.

[0115] The trapezoidal mounting block 303 has a trapezoidal groove for clamping and fixing with the end face of the truncated cone-shaped tubular structure 302. The position of the trapezoidal groove should meet the requirements of fixing with the end face of the first cylindrical tubular structure 301 and inserting the sheet 201 into the specified depth of the first cylindrical cavity. Specifically, one end of the trapezoidal mounting block 303 is connected to the end face of the first cylindrical tubular structure 301, and the other end is inserted into the interior of the first cylindrical tubular structure 301, and the sheet 201 is pressed into the first cylindrical cavity. After the trapezoidal mounting block 303 is inserted, the inner diameter of the trapezoidal mounting block 303 serves as the first air channel 101 through which the airflow passes. The inner diameter of the trapezoidal mounting block 303 is 16 mm, that is, the sheet 201 is set at the connection between the first air channel 101 and the second air channel 102. The radial direction of the sheet 201 is perpendicular to the airflow direction of the first air channel 101, and the axial direction of the through hole 202 is parallel to the airflow direction of the first air channel 101.

[0116] A handle is fixedly connected to the integrated tubular structure.

[0117] The first air channel 101 is used to transform laminar flow into turbulent flow; the sheet 201 is used to enhance the turbulence intensity and uniformity of the turbulent flow; the cross section of the second air channel 102 gradually narrows along the airflow direction, which is used to converge the turbulent flow and make it have higher turbulent kinetic energy; the third air channel 103 is used to guide the turbulent flow to be ejected.

[0118] The liquid supply device 400 uses a needleless syringe, the liquid outlet of the syringe is located on the central axis of the second cylindrical cavity, and the distance between the liquid outlet of the syringe and the outlet of the third airway 102 is 2 mm.

[0119] Equipment Example 2 It is basically the same as the device example 1, except that the number of through holes 202 on the sheet 201 is 10 and the size of the through holes remains unchanged.

[0120] Equipment Example 3 It is basically the same as the device example 1, except that the number of through holes 202 on the sheet 201 is 20, and the size of the through holes remains unchanged.

[0121] Equipment Example 4 It is basically the same as the device example 1, except that the length of the second air channel 102 is 15 mm.

[0122] Equipment Example 5 It is basically the same as the device example 1, except that the length of the second air channel 102 is 7 mm.

[0123] The corresponding relationship between Chinese and English in the present invention is shown in Table 2 below: Table 1

[0124] The spinning solution used in the embodiment of the present invention is as follows: Prepare a single-component spinning solution: dissolve solute 1 with a mass of m1 in a solvent with a mass of m, and stir at a temperature of t1 and a stirring speed of r1 until dissolved. The details are as follows: Table 2

[0125] Taking Example 1 as an example, the process of preparing the spinning solution is as follows: 8 g of PCL is dissolved in 92 g of DCM, and stirred at 60° C. at a stirring speed of 1000 rpm until dissolved to obtain a spinning solution.

[0126] Prepare a two-component spinning solution: Based on the above single-component spinning solution, continue to add solute 2 with a mass of m2, stir at temperature t2 and stirring speed r2 until it dissolves. The details are as follows: Table 3

[0127] Taking the two-component spinning solution No. 1B as an example, the process of preparing the spinning solution is as follows: 8 g of PCL is dissolved in 92 g of DCM, stirred at 60°C at a stirring speed of 1000 rpm until dissolved, and then 24 g of chitosan is added at a stirring speed of 1000 rpm and stirred at 25°C until dissolved to obtain a spinning solution.

[0128] Prepare a three-component spinning solution: Based on the above two-component spinning solution, continue to add solute 3 with a mass of m3, stir at temperature t3 and stirring speed r3 until it dissolves. The details are as follows: Table 4

[0129] Taking the three-component spinning solution No. 1C as an example, the process of preparing the spinning solution is as follows: 8 g of PCL is dissolved in 92 g of DCM, stirred at 60°C at a stirring speed of 1000 rpm until dissolved, 24 g of chitosan is added at a stirring speed of 1000 rpm until dissolved, and then 3 g of PEG is added at a stirring speed of 1000 rpm until dissolved to obtain a spinning solution.

[0130] The testing method of the present invention comprises: Average fiber diameter and average bending angle: The diameter and bending angle of 1000 curled microfibers from no less than 10 SEM photos were measured using Image Pro plus software (Media Cybernetics, USA), and the average value was calculated to obtain the average diameter and average bending angle of the curled microfibers. The bending angle was measured by selecting a microfiber with a length greater than or equal to 20 μm and selecting a 20 μm length, measuring the tangent direction a (vector) at the starting point of the length, and the tangent direction b (vector) at the end point of the length, and recording the deflection angle between the tangent direction a and the tangent direction b as the bending angle, as shown in the figure. Figure 22 shown.

[0131] Static contact angle: no water drop method, using the contact angle / surface tension measuring instrument OCA20 from Dataphysics, Germany.

[0132] Porosity: X-ray ultrafine computed tomography using the EasyTom XL from RX Solutions.

[0133] Example 1 A method for preparing a highly curled ultrafine fiber material, using the spinning device shown in the above-mentioned equipment example 1 for spinning; the specific process is as follows: The spinning solution No. 2A is placed in the syringe of Equipment Example 1, and the liquid supply rate v is set to 300 mL / h. The distance L between the liquid outlet of the syringe and the receiving device (rotating drum) is 30 cm. The spray gun is started and the syringe is pushed at a constant speed. The spinning solution is sheared in a convergent turbulent field with high turbulent kinetic energy and disorder. The folding and change frequency increases, the solvent evaporates, and the solute forms curled fibers, which are collected on the rotating drum to obtain curled ultrafine fiber material. The air flow velocity V is measured to be 18 m / s, and spinning begins; wherein, the air flow velocity V is extended along the axial direction of the third air channel and is measured at a position 75 mm away from the end face of the third air channel.

[0134] Examples 2 to 14 The method is basically the same as Example 1, except that the spinning solution No. 2A is replaced by the spinning solution corresponding to the following table.

[0135] Table 5

[0136] Comparative Example 1 The fiber of formula No. 3C was prepared using electrospinning technology and its physical properties were tested. The results are as follows: Electrospinning: The average curvature within a unit length of 20 microns is 20°~60°, the average bending angle is 17°, the average fiber diameter is 1225nm, the porosity is 70.85%, and the bulk density is 132.7mg / cm 3 , wettability 138.3°, no airflow intervention, no airflow turbulence kinetic energy.

[0137] Comparative Example 2 The fiber of formula No. 3C was prepared using ordinary air-spinning technology and its physical properties were tested. The results are as follows: Ordinary air-spun: The average curvature within a unit length of 20 microns is 90°~180°, the average bending angle is 77°, the average fiber diameter is 449nm, the porosity is 80.88%, and the bulk density is 12.34mg / cm 3 , wettability is 136.7°, the airflow is mainly laminar, and there is no turbulent kinetic energy.

[0138] In terms of fluffiness, the fibers prepared by the method of the present invention are the fluffiest, followed by conventional air spinning, and electrospinning is the worst.

[0139] Test Example 1 The ultrafine fiber materials deposited in each embodiment were subjected to a microstructure test. The test method was as follows: an appropriate amount of the dried fiber sample was cut, fixed on a conductive tape and pasted to the surface of the SEM sample stage. After gold spraying treatment, it was placed in a scanning electron microscope and imaged at an appropriate acceleration voltage to obtain images of the micromorphology and structural characteristics of the fiber.

[0140] The test results show that the nanofiber materials of Examples 1 to 14 are all porous structures, with an average bending angle of more than 220°, an average fiber diameter of less than 1 μm, a porosity of 90% to 99.999%, and a bulk density of 10 to 200 mg / cm³. Taking Example 3 as an example, its structure is as follows: Figure 8 Specifically, the performance parameters of the ultrafine fiber materials in Examples 1 to 3 are shown in the following table.

[0141] Table 6

[0142] According to the test results of the fibers obtained in the above embodiments, the average bending angles of the single-component, two-component and three-component spinning solutions are above 220°.

[0143] Test Example 2 The highly curled microfiber material of Example 3 was brought into contact with fresh blood and allowed to stand for 5 minutes to allow a preliminary cross-linking reaction to occur to form a three-dimensional network (gel). The viscosity of the three-dimensional network was tested using a rotary viscosity tester at 25°C. The gel was placed in a standard measuring cup, a suitable rotor was selected, and the viscosity value (unit: Pa·s) was read at a steady-state speed. Each group of samples was tested three times, and the average value was taken as the final viscosity coefficient. The test result was 20~50 Pa·s.

[0144] At the same time, the highly curled microfiber material of Example 3 was brought into contact with fresh blood and allowed to stand for 5 minutes to allow a preliminary cross-linking reaction to occur to form a three-dimensional network (gel). Unbound blood was then gently washed away with PBS, and the material was rapidly frozen and freeze-dried. Representative areas were then cut out and fixed on conductive tape, sprayed with gold, and placed under a scanning electron microscope. The SEM images of the partial cross-linking of the fiber network and blood were observed at an accelerating voltage of 5-10 kV, as shown in FIG. Figure 9 shown.

[0145] Test Example 3 The highly curled microfiber material of Example 3 was fully contacted with fresh blood and allowed to stand for 15 minutes until the material and blood were completely cross-linked to form a stable gel structure. Figure 10 The gel was then gently rinsed with PBS to remove unbound blood components. After freezing and freeze-drying, the gel area was cut and fixed on conductive tape. It was then sprayed with gold and placed under a scanning electron microscope. The image was taken at an accelerating voltage of 5-10kV to observe the three-dimensional network (i.e., blood gel) formed by the cross-linking of highly curled microfiber materials and blood. The SEM image is shown in the figure below. Figure 11 shown.

[0146] Furthermore, scanning electron microscopy (SEM) combined with energy spectrum elemental analysis (EDS mapping) was used to characterize the three-dimensional gel structure formed by the cross-linking of highly curled microfibers and blood. After the material was dried, SEM observation was performed directly, and element spectrum scanning was performed on the selected area under the premise of avoiding interference from foreign elements to obtain the distribution map of key elements such as C, O, N, Na, P, and Ca. Figure 12 The results show that blood components are evenly distributed in the fiber network, especially Na, P, Ca and other elements are enriched in the cross-linked area, indicating that the fiber can effectively capture blood components and form a stable three-dimensional gel structure, verifying its excellent blood compatibility and hemostatic properties. Among them, the schematic diagram of red blood cells in the three-dimensional network formed by the cross-linking of the highly curled microfiber material and blood is shown in Figure 2. Figure 13 shown.

[0147] Test Example 4 Fresh rat liver tissue was taken, the surface was rinsed with PBS and kept moist, and the liver tissue was used as the receiving substrate. The spinning solution and spinning parameters of Example 3 were used for spinning. The fiber material was sprayed to form a film and allowed to stand for 5 minutes to allow the fiber material to form a preliminary adhesion to the tissue surface. A universal material testing machine equipped with a 90° peeling fixture was used to fix the tissue and connect the material edges. The material was stretched at a speed of 1 mm / min. The force-displacement curve during the peeling process was recorded. Each group of tests was averaged 5 times. The obtained values ​​formed a curve as shown in the figure. Figure 14 As shown, according to the test data, the 90° peeling force between the curled microfiber material and the liver tissue is greater than or equal to 1 kPa.

[0148] Test Example 5 The wound surface after penetrating injury of the right lobe of rat liver was used as the receiving substrate, and the spinning solution and spinning parameters of Example 3 were used for spinning. After spinning for 20 seconds, the fiber material was sprayed to form a coating, so that the fiber material formed a preliminary adhesion with the tissue surface. The actual figure is shown in FIG. Figure 15 The photo of the rat liver's recovery after seven days is shown in Figures 16 and 17 shown.

[0149] Test Example 6 The stress-strain curves of the fiber materials obtained in Example 5 and Example 10 were tested. The fiber material corresponding to Example 5 is a curled ultrafine fiber material, and its corresponding curves are shown in FIG. Figure 18 As shown, the fiber material corresponding to Example 10 is a hemostatic material, and its corresponding curve is as shown in FIG. Figure 19 shown.

[0150] Experimental results demonstrate that despite being loaded with a large number of functional particles, the hemostatic fiber material maintains excellent mechanical properties, demonstrated by a significant increase in peak stress and only a slight decrease in ductility, with no apparent embrittlement. This indicates that the fiber material of this invention achieves high loading rates while maintaining high flexibility and toughness, contributing to improved stability, adaptability, and overall hemostatic effectiveness in practical hemostasis scenarios.

[0151] Test Example 7 The fiber materials obtained in Examples 5 and 10 were interacted with blood as follows Figure 20 As shown, the fiber material corresponding to Example 5 is a curled ultrafine fiber material, and the fiber material corresponding to Example 10 is a hemostatic material.

[0152] As can be seen from the figure, the hemostatic material forms a dense, stable gel upon interaction with blood, significantly outperforming the curly microfiber material in terms of exudation and gel-forming ability. This difference reflects the fiber network's superior structural adaptability and functional performance in absorbing blood, promoting coagulation, and sealing wounds, significantly improving hemostatic efficiency and material application stability.

[0153] Test Example 8 This experiment selected three different hemostatic fiber materials: an electrospun straight fiber hemostatic material (Comparative Example 1), an air-spun micro-curled fiber hemostatic material (Comparative Example 2), and a highly curly ultrafine fiber hemostatic material prepared using convergent end turbulence induction technology (Example 3). 0.08 g of each material was weighed and placed in separate transparent test tubes. An equal volume of blood was then added dropwise to the test tubes until the material was completely absorbed and no free blood remained in the tubes, thus reaching adsorption saturation. The mass of the test tubes after blood absorption was measured to calculate the mass of blood absorbed by each material.

[0154] The experimental results are as follows Figure 21 As shown in the test, the electrospun straight fiber material absorbed approximately 0.162 grams of blood, the air-spun micro-curled material absorbed approximately 0.336 grams of blood, and the highly curly microfiber material absorbed approximately 0.502 grams of blood. Under the same mass conditions, the highly curly microfiber exhibited the strongest blood absorption ability, approximately 3.1 times that of the straight fiber material. This result indicates that the three-dimensional curly structure of the fiber significantly increases the material's specific surface area and porosity, enhancing its ability to rapidly adsorb liquids and capture blood, helping to accelerate blood coagulation and improve hemostasis efficiency.

[0155] The mass of blood captured by the curled microfiber material is more than 600% of the mass of the curled microfiber.

[0156] Test Example 9 A method for preparing a hemostatic material, wherein the spinning device shown in the above-mentioned equipment example 1 is used for spinning; the specific process is as follows: The wound formed by stabbing the femoral artery in the rabbit's leg has not healed and blood is oozing.

[0157] The wound surface was used as the receiving substrate for the fiber, and spinning was performed using the spinning solution and spinning parameters of Example 3. After spinning for 20 seconds, the bleeding volume, hemostasis time, and healing status were tested. Specifically: Average bleeding volume: 3.15g.

[0158] Hemostasis time: 15s.

[0159] Healing condition: no blood oozing, hemostasis was successful.

[0160] Test Example 10 The rats' tails were amputated to simulate bleeding from human fingers. The experiment was divided into a blank control group (no hemostatic material) and an experimental group (hemostatic material). The hemostatic materials in the experimental group were: Experimental Group 1: The wound surface was used as the receiving substrate for the fibers, and spinning was performed using the spinning solution and spinning parameters of Example 3 for 20 seconds.

[0161] Experimental Group 2: The fibers in Comparative Example 1 had the same mass as the highly curled microfiber material prepared in Experimental Group 1.

[0162] Experimental Group 3: The fibers in Comparative Example 2 had the same mass as the highly curled microfiber material prepared in Experimental Group 1.

[0163] The amount of bleeding, hemostasis time and healing status within 3 minutes were compared between the blank control group and the experimental group. The results are as follows: Blank control group: The average bleeding volume within 3 minutes was 1.6g, the wound continued to bleed and healed slowly.

[0164] In the experimental group, a stable blood gel formed 10 seconds after spraying the hemostatic material of our invention, and the average bleeding volume was reduced to 0.2g within 3 minutes. Meanwhile, the bleeding volume of the electrospun fibers was 1.0g, while that of the conventional air-spun fibers was 0.7g. The rats recovered well, demonstrating that our material demonstrates excellent biocompatibility and tissue repair capabilities.

[0165] Test Example 11 The parameters of the airflow field formed by the spinning equipment of the above-mentioned equipment examples 1 to 5 are simulated under the pressure difference condition of one atmosphere. The simulation process is as follows: First, based on the geometric parameters of the integrated tubular structure in the aforementioned device example, a pipeline simulation model (i.e., models corresponding to the first, second, and third airways connected in sequence) was generated in Solidworks 3D modeling software. This pipeline model was then imported into meshing software (IECM) to obtain a mesh model of the pipeline. Using fluid dynamics methods, the mesh model was used to simulate the airflow in the pipeline and the high-speed airflow jet flow field at the nozzle outlet (i.e., the cross-section of the third airway). By extracting the Q isosurface of the flow field, the complex vortex structure of the airflow jet was obtained. Furthermore, fluid dynamic parameters such as velocity, pressure, density, and temperature of the gas at different locations along the flow path at the nozzle center (i.e., the center of the circle on the end face of the third airway) were extracted. The airflow velocity and turbulent kinetic energy at a distance of 80 cm from the nozzle were collected, as shown in Table 1 below.

[0166] Table 7

[0167] When the above-mentioned equipment examples 2 to 5 were used to replace the equipment example 1 in Example 1 for spinning, it was found that the average bending angle and other properties of the obtained fiber material were lower than those in Example 1.

[0168] In summary, the present invention achieves the preparation of in-situ highly curled ultrafine fibers by optimizing the spinning equipment and process, and combines it with a biopolymer cross-linking system to provide an efficient and stable hemostatic method. The high specific surface area and enhanced porosity of the in-situ highly curled ultrafine fibers ensure a rapid hemostatic effect, and can adapt to complex clinical environments such as high-pressure arterial bleeding, irregular wounds and deep wounds. Compared with traditional hemostatic materials, the curled ultrafine fibers of the present invention can more efficiently adsorb platelets and coagulation factors, accelerate the formation of blood gel, and complete the hemostatic process within 5 seconds to 2 minutes, while reducing blood loss and reducing the risk of secondary trauma.

[0169] The cross-linking degree of the hemogel can be controlled between 10% and 99%, ensuring excellent mechanical stability and biocompatibility in the body. The hemogel also exhibits adjustable adhesion properties, with an adhesion strength ranging from 1 to 200 kPa and a peel strength ranging from 0.01 to 5 N / cm. This allows for secure adhesion to wound surfaces without causing tissue damage due to excessive adhesion. Furthermore, the material's bulk density is controlled between 0.1 and 1.5 g / cm³, ensuring the hemostatic material's lightweight and excellent mechanical properties, further enhancing its practicality in medical emergency situations.

[0170] By adjusting the material formulation and preparation process, the present invention can meet personalized hemostasis requirements, such as varying coagulation rates, tissue repair capabilities, and antibacterial properties, making it highly adaptable in a variety of applications, including emergency medical care, battlefield rescue, disaster relief, and complex surgery. Furthermore, the present invention's spraying process, based on a portable handheld spray gun and combined with turbulence enhancement technology, improves the efficiency of ultrafine fiber preparation, supports large-scale production, and reduces manufacturing costs, making it an efficient, convenient, and economical hemostasis solution with broad industrial prospects.

[0171] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A curly ultrafine fiber material prepared by solution blowing technology, characterized in that: include: Curled nanofibers with an average fiber diameter less than 1 μm and an average bending angle greater than or equal to 220°.

2. The curled microfiber material according to claim 1, characterized in that: In the curly microfiber material, the curly microfibers with a bending angle of greater than or equal to 250° account for more than 50% of the total number of fibers, preferably more than 60%; And / or, the average fiber diameter of the curled nanofibers is 10 to 800 nm, preferably 50 to 600 nm, more preferably 100 to 550 nm, and more preferably 200 to 500 nm.

3. The curled microfiber material according to claim 1 or 2, characterized in that: The porosity of the curled ultrafine fiber material is 90% to 99.999%, preferably 90% to 99%, further preferably 90% to 95%, and more preferably 90% to 92%; And / or, the volume density of the curled ultrafine fiber material is 10~200 mg / cm³, preferably 10~100 mg / cm³, further preferably 10~50 mg / cm³, and more preferably 10~20 mg / cm³.

4. The curled ultrafine fiber material according to any one of claims 1 to 3, characterized in that: The curled ultrafine fiber matrix is ​​a soluble polymer; Preferably, the soluble polymer is one or a combination of two or more of a degradable polymer, PMMA, PVB, and PU; the degradable polymer may preferably be one or a combination of two or more of PCL, PLA, and PLGA; and / or, the curled nanofibers optionally include a functional component; The functional component is preferably one or a combination of two or more selected from the group consisting of hydrophilic modified polymers, natural polymers, coagulant proteins, sodium alginate, and inorganic particles; the hydrophilic modified polymer is preferably one or a combination of two or more selected from the group consisting of polyethylene oxide and polyethylene glycol; the natural polymer is preferably one or a combination of two or more selected from the group consisting of chitosan, collagen, and cellulose, and more preferably chitosan; the inorganic particles are preferably inorganic nanoparticles, and more preferably one or a combination of two or more selected from the group consisting of silicon dioxide nanoparticles, zinc oxide nanoparticles, and silver nanoparticles, and even more preferably silver sulfadiazine powder; Further preferably, the content of the functional component is more than 30% of the mass of the polymer, more preferably more than 50%, more than 100%, more than 200%, more than 300%; and / or, the content of the hydrophilic modified polymer is more than 30% of the mass of the curled nanofiber, more preferably more than 35%, more than 40%, more than 45%.

5. The method for preparing the curled ultrafine fiber material according to any one of claims 1 to 4, characterized in that: include: It is made from spinning solution using solution blowing technology; The spinning equipment used in the solution blowing technology includes a spray gun and a liquid supply device (400); The spray gun comprises: An air supply device, used for forming an airflow, wherein the airflow is a horizontal flow; A cavity, comprising: a first air channel (101), connected to the air supply device; a second air channel (102), communicating with the first air channel (101); a third airway (103), communicating with the second airway (102); A sheet (201) having at least two through holes (202) and disposed in the cavity; The first air channel (101) is used to form turbulence, the sheet (201) is used to enhance the intensity and uniformity of the turbulence, the cross section of the second air channel (102) is gradually narrowed along the airflow direction, and is used to converge the turbulence; the third air channel (103) is used to guide the converged turbulent flow to be ejected; The liquid supply direction of the liquid supply device (400) intersects with the direction of the airflow ejected from the spray gun; preferably, the intersection of the extension line of the liquid supply direction of the liquid supply device (400) and the extension line of the direction of the airflow ejected from the spray gun is located 0.1~5 cm in front of the outlet end of the spray gun; further preferably, the liquid outlet of the liquid supply device (400) is located on the central axis of the third air channel (103), and the distance d from the outlet of the third air channel (103) is 0.1~5 cm, and further preferably, the distance d is 0.1~2 cm, 0.15~1.5 cm, or 0.2~1 cm.

6. The preparation method according to claim 5, characterized in that: The airflow formed by the spray gun is simulated under the pressure difference of one atmosphere, and the airflow velocity at 80 cm from the outlet of the third air channel (103) is greater than or equal to 190 m / s; the turbulent kinetic energy at 45 mm from the outlet of the third air channel (103) is greater than or equal to 1500 kg / (m×s 2 ).

7. The preparation method according to claim 5, characterized in that: The sheet (201) comprises: a circular gasket provided with more than 37 through holes (202), and further preferably, protrusions and / or grooves are formed on the inner walls of the through holes (202) along the airflow direction; And / or, the radial direction of the circular gasket is perpendicular to the airflow direction of the first air duct (101), and the axial direction of the through hole (202) is parallel to the airflow direction of the first air duct (101).

8. The preparation method according to claim 7, characterized in that: The thickness of the circular gasket is in the range of 2-5 mm, and the distance between two adjacent through holes is in the range of 0.1-3 mm.

9. The preparation method according to claim 5, characterized in that: The air flow velocity V is greater than 18 m / s when measured at a position 6 mm away from the central axis on a cross section at a position 75 mm from the end face of the third air channel (103) along the axial extension of the central axis of the third air channel (103).

10. The preparation method according to claim 5, characterized in that: The sheet (201) is provided at the first airway (101), the second airway (102), or at the connection between the first airway (101) and the second airway (102).

11. The preparation method according to claim 5, characterized in that: Also includes: One-piece tubular structure, including: A cylindrical tubular structure (301), wherein the first airway (101) formed inside the cylindrical tubular structure is a circular tubular channel; A truncated cone-shaped tubular structure (302) is an integral structure with the cylindrical tubular structure (301), and the second air channel (102) and the third air channel (103) are sequentially formed inside the truncated cone-shaped tubular structure (302) along the airflow direction; A trapezoidal mounting block (303) has one end connected to the end surface of the cylindrical tubular structure (301) and the other end inserted into the interior of the cylindrical tubular structure (301) to press the sheet (201) into the cavity.

12. The preparation method according to claim 11, characterized in that: The inner diameter of the cylindrical tubular structure (301) and the inner diameter of the bottom surface of the truncated cone-shaped tubular structure (302) are the same, and the value range is 1~10 cm; the height of the cylindrical tubular structure (301) is in the range of 5~25 cm, preferably 5~20 cm, 5~15 cm, 6~12 cm, and 6~10 cm; the height of the truncated cone-shaped tubular structure (302) is in the range of 1~5 cm, preferably 1~4 cm, 1~3 cm, and 1~2 cm; the inner diameter of the top surface of the truncated cone-shaped tubular structure (302) is in the range of 3~10 mm, preferably 3~8 mm, 3~6 mm, 3~5 mm, and 4 mm.

13. A hemostatic material, characterized in that: The invention comprises the curled ultrafine fiber material according to any one of claims 1 to 4, or the curled ultrafine fiber material prepared by the preparation method according to any one of claims 5 to 12.

14. The hemostatic material according to claim 13, characterized in that: The 90° peeling force between the curled microfiber material and the liver tissue is 1-5 kPa.

15. The curled microfiber material according to claim 13, characterized in that: Also includes: The blood captured by the crimped ultrafine fiber material forms a three-dimensional network integral with the crimped ultrafine fibers.

16. The hemostatic material according to claim 14 or 15, characterized in that: The mass of blood captured by the curled microfiber material is more than 600% of the mass of the curled microfiber.

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