Silver-loaded metakaolin hemostatic sponge and preparation method thereof

Abstract

The invention discloses a silver-loaded metakaolin hemostatic sponge and a preparation method thereof. The silver-loaded metakaolin hemostatic sponge uses a foaming material as a base material, wherein the base material includes a mixed material of silver-loaded metakaolin and zeolite and short-cut fibers that are compatible with the human body. The silver-loaded metakaolin hemostatic sponge of the invention has good adsorption and comprehensive hemostatic effects, and different types of silver-loaded metakaolin hemostatic sponges can be used for wounds in different recovery stages to accelerate the healing process. The short-cut silk fibers not only increase the biocompatibility of the material, but also reduce the shedding of exposed particles at the cut surface, thereby preventing other potential hazards to the human body while implementing the hemostatic effect.

Description

Technical Field

[0001] The invention relates to the technical field of hemostatic materials, in particular to a silver-loaded metakaolin hemostatic sponge and a preparation method thereof. Background Art

[0002] During surgery or emergency treatment, uncontrolled heavy bleeding can lead to a series of adverse reactions in the body, even shock and death. Furthermore, wound infection caused by failure to quickly stop bleeding can also cause local changes in the body or pathological reactions such as systemic poisoning. Therefore, the key to preventing bleeding injuries and even death lies in safe, effective, and rapid hemostasis.

[0003] Traditional methods for rapid hemostasis include topical hemostatic materials, direct compression, suturing, and electrocoagulation. With advancements in topical hemostatic materials, their effectiveness has improved, and their applications are expanding. Topical hemostatic materials include coagulation-promoting powders, gels, and sponges. Among these, patches such as gelatin sponges and oxidized cellulose, which act directly on bleeding wounds, offer immediate hemostatic effects and are widely used clinically.

[0004] A Chinese patent application, CN201811285479.2, titled "A Highly Absorbent Silk Fibroin Hemostatic Membrane and Its Preparation Method," discloses a highly absorbent silk fibroin hemostatic membrane and its preparation method. The membrane comprises polyethylene oxide, silk fibroin, sodium alginate, and nano-silica. It exhibits excellent hemostatic effects, can absorb large amounts of wound exudate, and has good air permeability and biocompatibility. This invention primarily utilizes the excellent air permeability and moisture retention of silk fibroin to promote rapid wound healing, and nano-silica is capable of effectively absorbing water from the blood. Overall, due to the lack of hemostatic components, its overall hemostatic effect needs to be improved.

[0005] Chinese patent application number JP2008548807, entitled "Hemostatic Device Containing Adsorbent," discloses a hemostatic material composed of a porous carrier and an adsorbent, such as molecular sieves or diatomaceous earth, glass powder or glass fiber, precipitated silica or fumed silica, kaolin and montmorillonite clay, and calcium-exchanged palm shell. Combined with inorganic materials, this material forms a hemostatic device that can more effectively treat mammalian wounds. Compared to applying zeolite directly to the skin, these hemostatic devices can reduce skin temperature rise. While this material exhibits good hemostatic effects, it may also suffer from issues such as insufficient human compatibility and shedding of adsorbent particles from the material's surface.

[0006] In view of this, it is necessary to develop a hemostatic material with good affinity, good adsorption effect and low particle shedding rate on the material surface. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a silver-loaded metakaolin hemostatic sponge and a preparation method thereof in view of the deficiencies in the above-mentioned prior art.

[0008] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: the present invention provides a silver-loaded metakaolin hemostatic sponge, which uses a foaming material as a base material, and the base material includes a mixed material of silver-loaded metakaolin and zeolite and short-cut fibers that are compatible with the human body;

[0009] The addition ratio of the silver-loaded metakaolin and zeolite mixed material is 10 wt%-40 wt%; the addition ratio of the chopped fibers is 3 wt%-15 wt%.

[0010] Preferably, the chopped fibers include degummed silk fibers.

[0011] Preferably, the silver-loaded metakaolin hemostatic sponge includes at least the following types based on the mass ratio of zeolite to metakaolin and the different functions:

[0012] Type A: Suitable for hemostasis or the early stage of high exudation of wound inflammation, wherein the mixture of silver-loaded metakaolin and zeolite has a zeolite:metakaolin ratio of (1.5-3):1;

[0013] Type B: Suitable for the granulation growth stage of wound inflammation in the middle stage, wherein the silver-loaded metakaolin and zeolite mixed material has a zeolite:metakaolin ratio of (0.8-1.5):1;

[0014] Type C: Suitable for the epithelialization stage in the later stage of wound repair, wherein the silver-loaded metakaolin and zeolite mixed material has a zeolite:metakaolin ratio of (0.3-0.8):1.

[0015] A method for preparing a silver-loaded metakaolin hemostatic sponge comprises the following steps:

[0016] S1. 100 parts of polyol, 1-3 parts of water, 6-15 parts of additives, 35-85 parts of silver-loaded metakaolin and zeolite mixed material, 10-25 parts of chopped fibers and 110-150 parts of isocyanate were sequentially put into a blender and mixed and foamed to obtain a silver-loaded metakaolin hemostatic sponge embryo;

[0017] S2. Cut the original embryo of the silver-loaded metakaolin hemostatic sponge to the desired thickness to obtain a slice of the original embryo of the silver-loaded metakaolin hemostatic sponge;

[0018] S3. After cutting, hot pressing is performed on at least one side of the slice of the silver-loaded metakaolin hemostatic sponge embryo to fix the particles exposed at the cut surface. After a second cutting, the sheet-shaped silver-loaded metakaolin hemostatic sponge of the desired specifications is obtained.

[0019] Preferably, the preparation method of the silver-loaded metakaolin and zeolite mixed material is:

[0020] The mixed material of metakaolin and zeolite is dry-milled in a ball mill for 30-60 minutes, wherein the mass ratio of zeolite to metakaolin is 0.3-3. Then, the silver ion solution is poured into the ball mill and wet-milled for 40-120 minutes to allow the silver ions to fully and evenly adhere to the surface of the metakaolin and zeolite particles. Then, the mixed material is dried at 50-80°C. Since the dried material is easy to agglomerate, the dried material is ball-milled again for 20-30 minutes to disperse it and then set aside.

[0021] Preferably, in S2, the silver-loaded metakaolin hemostatic sponge embryo is cut at a blade angle of 15-20°.

[0022] Preferably, in S2, the cutting speed is no more than 2 m / min to reduce edge tearing and form chopped fiber burrs at the cut surface.

[0023] Preferably, the fiber length of the chopped fibers is 0.5-5 mm, and the average fiber length of the chopped fibers is not greater than the thickness of the silver-loaded metakaolin hemostatic sponge embryo slice, so as to increase the number of chopped fibers and form more chopped fiber protrusions on the cross section of the silver-loaded metakaolin hemostatic sponge embryo slice.

[0024] Preferably, in S2, a roller press with a surface temperature of 120-130°C is used to roll the surface of one side of the silver-loaded metakaolin hemostatic sponge embryo slice, and the rolling pressure is 800-1200Pa. Subsequently, the silver-loaded metakaolin hemostatic sponge embryo slice is statically pressed for 5-10s at 80-100°C, and the static pressure is 1000-2000Pa.

[0025] Preferably, the auxiliary agent includes a physical foaming agent, a catalyst and a surfactant.

[0026] The present invention has at least the following advantages:

[0027] 1. Metakaolin can concentrate blood components, increase the relative concentration of local coagulation factors in bleeding areas, accelerate blood coagulation, and achieve a hemostatic effect; Zeolite has a more outstanding hemostatic effect, but the heat generated during the hemostatic process may cause burns. However, after being fully mixed with metakaolin in a certain proportion, combined with the heat conduction and heat absorption effects of the sponge matrix and silk fibers, it can effectively solve the problem of fever and achieve a better comprehensive hemostatic effect; at the same time, in addition to the hemostatic function, using different types of silver-loaded metakaolin hemostatic sponges for wounds in different recovery stages can better meet the wound treatment requirements at different stages and accelerate the healing process.

[0028] 2. By attaching silver ions to the surface of kaolin and zeolite, the silver-loaded metakaolin hemostatic sponge produced has a good and long-lasting antibacterial effect, and is effective against a variety of bacteria, fungi and other microorganisms, can avoid wound infection, reduce inflammatory response, and promote wound healing.

[0029] 3. The silver-loaded metakaolin hemostatic sponge of the present invention also has a good effect on the recovery of inflammatory exudative wounds: since the porous structure of the polyurethane sponge can effectively absorb exudate and reduce local accumulation; the silver ions released by the silver-loaded kaolin have a broad-spectrum antibacterial effect, which helps to control wound infection; at the same time, the zeolite can not only absorb odor and corrupt substances in the exudate, but also balance the wound microenvironment, preventing the overly acidic or overly alkaline skin environment from affecting wound healing; in addition, after moderate adsorption by the silver-loaded metakaolin hemostatic sponge, the wound surface protected by the silver-loaded metakaolin hemostatic sponge can remain moist without excessive drying, which is very beneficial to cell regeneration and tissue repair.

[0030] 4. The chopped silk fibers not only increase the biocompatibility of the material and improve the tensile strength of the sponge, but also make the protruding fibers on the cut surface fall down and stick to the cut surface through hot pressing, increasing the coverage area of ​​the fibers on the cut surface, binding the particles exposed on the cut surface, better reducing the risk of falling off, and effectively preventing other potential hazards to the human body while implementing the hemostatic effect. DETAILED DESCRIPTION

[0031] The present invention is further described in detail below with reference to the embodiments so that those skilled in the art can implement the invention with reference to the description.

[0032] It should be understood that terms such as “having”, “including” and “comprising” used herein do not preclude the existence or addition of one or more other elements or combinations thereof.

[0033] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Materials and reagents used in the following examples are commercially available unless otherwise specified. In the following examples, where specific conditions are not specified, the experiments were conducted under conventional conditions or those recommended by the manufacturer. Reagents and instruments used, where the manufacturer is not specified, are commercially available conventional products.

[0034] A silver-loaded metakaolin hemostatic sponge has a foaming material as a base material, in which a mixed material of silver-loaded metakaolin and zeolite and short-cut fibers compatible with the human body are embedded. Compared with kaolin, the mixed material of silver-loaded metakaolin and zeolite can achieve a better comprehensive hemostatic effect.

[0035] The silver-loaded metakaolin and zeolite mixture is added in a ratio of 10-40 wt%; the chopped fibers are added in a ratio of 3-15 wt%. The metakaolin, with a particle size of 1.5 μm or greater, has high adsorption properties and can quickly absorb water and red blood cells from the blood to form blood clots, accelerating the body's natural blood coagulation. It can also activate coagulation factor XII, initiating the coagulation cascade. It also has good biocompatibility, does not cause severe tissue reactions, and has certain antibacterial properties.

[0036] The chopped fibers are made of degummed mulberry silk. Silk fibers have good biocompatibility and are more compatible with the human body. Compared to tussah silk, mulberry silk is thinner and easier to shape.

[0037] In practical applications, silver-loaded metakaolin hemostatic sponges are distinguished by the mass ratio of zeolite and metakaolin and their functions. The silver-loaded metakaolin hemostatic sponges include at least the following types:

[0038] Type A: Suitable for hemostasis or the high exudate stage in the early stages of wound inflammation. The silver-loaded metakaolin and zeolite mixture has a zeolite:metakaolin ratio of (1.5-3):1. The strong adsorption properties of the zeolite's porous structure allow for rapid adsorption of blood to achieve rapid hemostasis. When used in the high exudate stage of wound inflammation, it can absorb large amounts of exudate over a period of time while rapidly releasing silver ions to inhibit infection. A certain dose of silver ions (e.g., 50 ppm) can provide long-term bactericidal effects. However, if used over a longer period of time, excessive silver ion concentrations should be avoided to inhibit fibroblast migration. However, if used for short-term hemostasis, high doses of silver will not have significant side effects on the human body. Therefore, products with concentrations far higher than 50 ppm (e.g., 1000 ppm) can be used for rapid bactericidal effects. Since type A silver-loaded metakaolin hemostatic sponge contains more zeolite, the heat generation can be significantly reduced due to the effect of metakaolin and the addition of foaming matrix and chopped fibers. Even if the ratio of zeolite: metakaolin = 3:1 is used, the temperature acting on the wound when used at room temperature will generally not exceed 45°C.

[0039] Type B: Suitable for the granulation growth stage of mid-stage wound inflammation, wherein the silver-loaded metakaolin and zeolite mixture material has a zeolite:metakaolin ratio of (0.8-1.5):1; the silver-loaded metakaolin and zeolite mixture material at this ratio can balance the adsorption and healing functions, zeolite continuously absorbs and controls bacteria, kaolin promotes collagen deposition, and shortens the healing period.

[0040] Type C: Suitable for the late epithelialization stage of wound repair. This silver-loaded metakaolin and zeolite mixture has a zeolite:metakaolin ratio of (0.3-0.8):1. This silver-loaded metakaolin and zeolite mixture accelerates angiogenesis by increasing the kaolin content, preventing excessive adsorption and wound dehydration. Since scabs have already formed at this stage, silver-loaded metakaolin hemostatic sponges with low or no silver content are sufficient.

[0041] A method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, comprising the following steps:

[0042] S1. 100 parts of polyol, 2 parts of water, 12 parts of additives, 60 parts of a mixed material of silver-loaded metakaolin and zeolite, 15 parts of chopped fibers, and 130 parts of isocyanate are sequentially put into a blender, mixed, and then foamed to obtain a silver-loaded metakaolin hemostatic sponge embryo; the additives include 0.5 parts of an amine catalyst (PC-5), 1.5 parts of silicone oil, and 10 parts of cyclopentane.

[0043] S2. Cut the original embryo of the silver-loaded metakaolin hemostatic sponge to the desired thickness to obtain a slice of the original embryo of the silver-loaded metakaolin hemostatic sponge;

[0044] S3. After cutting, hot pressing is performed on at least one side of the silver-loaded metakaolin hemostatic sponge embryo slice to fix the particles exposed at the cut surface. After a second cut, a sheet of silver-loaded metakaolin hemostatic sponge of the desired specifications is obtained. The cut surface will have a large number of kaolin and other particles exposed due to cutting. Hot pressing melts the foaming substrate at the cut surface and combines with the exposed particles to achieve the effect of fixing the cut surface particles and preventing powder loss. However, melting the foaming substrate at the cut surface will slow the absorption of blood by the silver-loaded metakaolin hemostatic sponge during hemostasis. Therefore, it is advisable to use a method that does not melt the foaming substrate or does not cause large-scale melting to fix the cut surface particles.

[0045] The preparation method of the silver-loaded metakaolin and zeolite mixed material is as follows:

[0046] Kaolin and zeolite are mixed in a mass ratio of 1:2 and dry-milled in a ball mill for 60 minutes. (The high adsorption properties of zeolite and kaolin can quickly absorb water from the blood, concentrating blood components, increasing the relative concentration of coagulation factors in the bleeding area, accelerating blood coagulation, and achieving a hemostatic effect.) Then, a silver nitrate aqueous solution (silver ion is one of the metal ions with the strongest bactericidal and antibacterial activity, with excellent antibacterial properties, capable of killing a variety of bacteria, fungi, and other microorganisms) is poured into the kaolin and zeolite mixture in a certain proportion (for example, to ultimately achieve a silver nitrate content of 60-120 mg per cubic decimeter of silver-loaded metakaolin hemostatic sponge). The mixture is then wet-milled for 60 minutes to ensure that the silver ions are fully and evenly attached to the surfaces of the metakaolin and zeolite particles. The mixture is then dried at 80°C. Because the dried material tends to clump easily, it is ball-milled again for 30 minutes to disperse it before use.

[0047] In S2, a silver-loaded metakaolin hemostatic sponge embryo was cut using a tungsten steel blade at a 20° blade angle. In S2, the cutting speed was 2 m / min to minimize edge tearing and form chopped fiber burrs at the cut surface. At this cutting angle, the cutting speed was minimized to allow a portion of the chopped fibers to be severed at the cut surface while allowing more of the ends of the remaining chopped fibers to be pulled out of the substrate. This portion of the chopped fibers formed chopped fiber burrs that were exposed at the cut surface. The more chopped fiber burrs, the better the particle fixation effect after heat pressing and lodging.

[0048] The fiber length of the chopped fibers is 0.5-5 mm, and the average fiber length of the chopped fibers is not greater than the thickness of the silver-loaded metakaolin hemostatic sponge embryo slice, so as to increase the number of chopped fibers and form more chopped fiber thorns on the cross section of the silver-loaded metakaolin hemostatic sponge embryo slice.

[0049] In S2, a roller press is used to press the surface of one side of the silver-loaded metakaolin hemostatic sponge embryo slice. The roller surface speed can be 1-2 m / min, the roller pressure is 1000 Pa, and the roller surface temperature is 120-130°C. This softens the silk fibers and allows them to adhere to the surface of the silver-loaded metakaolin hemostatic sponge embryo slice. Subsequently, the silver-loaded metakaolin hemostatic sponge embryo slice is statically pressed at 80-100°C for 5-10 seconds at a static pressure of 1000-2000 Pa, thereby shaping the silk fibers on the surface of the silver-loaded metakaolin hemostatic sponge embryo slice. This can control the powder shedding rate on the surface of the silver-loaded metakaolin hemostatic sponge embryo slice to below 0.5%.

[0050] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A method for preparing a silver-loaded metakaolin hemostatic sponge, characterized in that: The steps include: S1. 100 parts of polyol, 1-3 parts of water, 6-15 parts of additives, 35-85 parts of silver-loaded metakaolin and zeolite mixed material, 10-25 parts of chopped fibers and 110-150 parts of isocyanate were sequentially put into a blender and mixed and foamed to obtain a silver-loaded metakaolin hemostatic sponge embryo; S2. Cut the original embryo of the silver-loaded metakaolin hemostatic sponge to the desired thickness to obtain a slice of the original embryo of the silver-loaded metakaolin hemostatic sponge; S3 hot pressing after cutting, at least one side of the surface of the original embryo slice of silver-loaded metakaolin hemostatic sponge was hot pressed to fix the particles exposed at the cut surface, and after the second cutting, the desired specifications of the sheet silver-loaded metakaolin hemostatic sponge were obtained; In S2, the silver-loaded metakaolin hemostatic sponge embryo was cut at a blade angle of 15-20°; In S2, the cutting speed is not more than 2 m / min to reduce edge tearing and form short fiber burrs at the cut surface.

2. The method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, wherein: The preparation method of the silver-loaded metakaolin and zeolite mixed material is as follows: The mixed material of metakaolin and zeolite is dry-milled in a ball mill for 30-60 minutes, wherein the mass ratio of zeolite to metakaolin is 0.3-3. Then, the silver ion solution is poured into the ball mill and wet-milled for 40-120 minutes to allow the silver ions to fully and evenly adhere to the surface of the metakaolin and zeolite particles. Then, the mixed material is dried at 50-80°C. Since the dried material is easy to agglomerate, the dried material is ball-milled again for 20-30 minutes to disperse it and then set aside.

3. The method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, wherein: The fiber length of the chopped fibers is 0.5-5 mm, and the average fiber length of the chopped fibers is not greater than the thickness of the silver-loaded metakaolin hemostatic sponge embryo slice, so as to increase the number of chopped fibers and form more chopped fiber thorns on the cross section of the silver-loaded metakaolin hemostatic sponge embryo slice.

4. The method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, wherein: In S2, a roller press with a surface temperature of 120-130°C is used to roll the surface of one side of the silver-loaded metakaolin hemostatic sponge embryo slice at a rolling pressure of 800-1200Pa. Subsequently, the silver-loaded metakaolin hemostatic sponge embryo slice is statically pressed at 80-100°C for 5-10s at a static pressure of 1000-2000Pa.

5. The method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, wherein: The auxiliary agents include physical foaming agents, catalysts and surfactants.

6. A silver-loaded metakaolin hemostatic sponge prepared by the method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, characterized in that: The silver-loaded metakaolin hemostatic sponge uses a foaming material as a base material, wherein the base material includes a mixed material of silver-loaded metakaolin and zeolite and short-cut fibers that are compatible with the human body; The addition ratio of the silver-loaded metakaolin and zeolite mixed material is 10wt%-40wt%; the addition ratio of the chopped fibers is 3wt%-15wt%.

7. The silver-loaded metakaolin hemostatic sponge according to claim 6, characterized in that The chopped fibers include degummed silk fibers.

8. The silver-loaded metakaolin hemostatic sponge according to claim 6, characterized in that The silver-loaded metakaolin hemostatic sponges are distinguished by the mass ratio of zeolite to metakaolin and by their functions, and include at least the following types: Type A: Suitable for hemostasis or the high exudation stage in the early stage of wound inflammation, wherein the silver-loaded metakaolin and zeolite mixed material has a zeolite:metakaolin ratio of (1.5-3):1; Type B: Suitable for the granulation growth stage of wound inflammation in the middle stage, wherein the zeolite:metakaolin ratio of the mixed material of silver-loaded metakaolin and zeolite is (0.8-1.5):1; Type C: Suitable for the epithelialization stage in the later stage of wound repair, in which the silver-loaded metakaolin and zeolite mixed material has a zeolite:metakaolin ratio of (0.3-0.8):1.