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 takes a foaming material as a base material, and the base material comprises chopped fibers embedded with a silver-loaded metakaolin and zeolite mixed material and compatible to a human body; the silver-loaded metakaolin hemostatic sponge disclosed by the invention has good adsorbability and comprehensive hemostatic effect, and silver-loaded metakaolin hemostatic sponges of different models can be used for wounds in different recovery periods so as to accelerate the healing progress; the chopped silk fiber not only increases the biocompatibility of the material, but also can reduce the falling of exposed particles at the section, and prevents other potential hazards to the human body when the hemostatic effect is implemented.

Description

Technical Field

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

[0002] During surgery or first aid, if there is a large amount of uncontrollable bleeding, it may lead to a series of adverse reactions in the human body, and even cause shock and death. In addition, wound infections caused by the inability to stop bleeding quickly can also cause pathological reactions of local changes or systemic poisoning in the human body. Therefore, the key to preventing bleeding injuries and even death lies in safe and effective rapid hemostasis.

[0003] Traditional rapid hemostasis methods include local hemostatic materials, direct compression, suture, and electrocoagulation. With the progress of local hemostatic materials, the hemostatic effect is getting better and the application is increasing; local hemostatic materials include powders, gels, sponges, etc. that promote blood coagulation. Among them, patches such as gelatin sponge and oxidized cellulose that directly act on the bleeding wound surface have an immediate hemostatic effect and are widely used clinically.

[0004] In the Chinese patent with the application number CN201811285479.2 and the title "A highly absorbent silk fibroin hemostatic film and its preparation method", a highly absorbent silk fibroin hemostatic film and its preparation method are disclosed. The hemostatic film includes polyethylene oxide, silk fibroin, sodium alginate, and nano-silica. It has a good hemostatic effect, can absorb a large amount of wound exudate, and has good air permeability and biocompatibility. This invention mainly utilizes the good air permeability and moisture retention of silk fibroin, which can promote the rapid healing of wounds. And nano-silica can well absorb the moisture in the blood. Overall, due to the lack of hemostatic components, its overall hemostatic effect needs to be strengthened.

[0005] In the Chinese patent with the application number JP2008548807 and the title "Hemostatic device containing an adsorbent", a hemostatic material composed of a porous carrier and an adsorbent is disclosed. The adsorbent is, for example, molecular sieve or diatomaceous earth, glass powder or glass fiber, precipitated silica or fumed silica, kaolin and montmorillonite clay, and Ca-exchanged palm shell. Forming a hemostatic device in combination with inorganic substances can more effectively treat the wounds of mammals. Compared with directly applying zeolite on the skin, these hemostatic devices can reduce skin temperature rise. This material has a good hemostatic effect, but there may be problems of insufficient human compatibility and shedding of adsorbent particles on the material surface.

[0006] In view of this, it is necessary to develop a hemostatic material with good affinity, good adsorption effect, and low shedding rate of particles 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] To solve the above technical problems, the technical solution adopted by the present invention is: 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 mixture 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 mixture is 10wt%-40wt%; the addition ratio of the short-cut fibers is 3wt%--15wt%.

[0010] Preferably, the short-cut fibers include degummed silk fibers.

[0011] Preferably, according to the mass ratio and different functions of zeolite and metakaolin, the silver-loaded metakaolin hemostatic sponge is at least divided into the following types:

[0012] Type A: Suitable for the high-exudation stage of hemostasis or the initial stage of wound inflammation. Among them, the zeolite:metakaolin of the silver-loaded metakaolin and zeolite mixture is (1.5-3):1;

[0013] Type B: Suitable for the granulation growth stage of the middle stage of wound inflammation. Among them, the zeolite:metakaolin of the silver-loaded metakaolin and zeolite mixture is (0.8-1.5):1;

[0014] Type C: Suitable for the epithelialization stage of the late stage of wound repair. Among them, the zeolite:metakaolin of the silver-loaded metakaolin and zeolite mixture is (0.3-0.8):1.

[0015] A preparation method of a silver-loaded metakaolin hemostatic sponge includes the following steps:

[0016] S1. Sequentially put 100 parts of polyol, 1-3 parts of water, 6-15 parts of auxiliary agent, 35-85 parts of a mixture of silver-loaded metakaolin and zeolite, 10-25 parts of short-cut fibers, and 110-150 parts of isocyanate into a mixer, mix well and then foam to obtain a silver-loaded metakaolin hemostatic sponge blank;

[0017] S2. Cut the silver-loaded metakaolin hemostatic sponge blank according to the required thickness to obtain a silver-loaded metakaolin hemostatic sponge blank slice;

[0018] S3. After cutting, perform hot pressing treatment, at least on one surface of the silver-loaded metakaolin hemostatic sponge blank slice, to fix the particles exposed at the cut surface, and obtain a sheet-shaped silver-loaded metakaolin hemostatic sponge of the required specification after secondary cutting.

[0019] Preferably, the preparation method of the silver-loaded metakaolin and zeolite mixture is as follows:

[0020] Dry grind the mixture of metakaolin and zeolite in a ball mill for 30 - 60 min, where the mass ratio of zeolite to metakaolin is 0.3 - 3. Then pour the silver ion solution into the ball mill for wet grinding for 40 - 120 min to make the silver ions fully and evenly adhere to the surfaces of metakaolin and zeolite particles. Then dry at 50 - 80 °C. Since the dried material is prone to caking, finally, re-ball mill the dried material for 20 - 30 min for dispersion and use.

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

[0022] Preferably, in S2, the cutting speed is not greater than 2 m / min to reduce edge tearing and form short cut fiber barbs at the cut surface simultaneously.

[0023] Preferably, the fiber length of the short cut fibers is 0.5 - 5 mm, and the average fiber length of the short cut fibers is not greater than the thickness of the silver-loaded metakaolin hemostatic sponge blank slice to increase the number of short cut fibers and form more short cut fiber barbs at the cut surface of the silver-loaded metakaolin hemostatic sponge blank slice.

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

[0025] Preferably, the additives include physical foaming agents, catalysts, and surfactants.

[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 at the bleeding site, accelerate blood coagulation, and achieve a hemostatic effect. Zeolite has a more excellent hemostatic effect, but heat generation during the hemostasis process may cause burns. However, after being fully mixed with metakaolin in a certain proportion, together with the heat conduction and heat absorption effects of the sponge matrix and silk fibers, the problem of heat generation can be well solved, and a better comprehensive hemostatic effect can be achieved. At the same time, in addition to the hemostatic function, using silver-loaded metakaolin hemostatic sponges of different models for wounds in different recovery periods can better meet the requirements for wound treatment at different times and accelerate the healing progress.

[0028] 2. By attaching silver ions to the surfaces of kaolin and zeolite, the prepared silver-loaded metakaolin hemostatic sponge has good and long-lasting antibacterial effects, acts on various microorganisms such as bacteria and fungi, can avoid wound infections, reduce inflammatory reactions, and promote wound healing.

[0029] 3. The silver-loaded metakaolin hemostatic sponge of the present invention also has good effects on the recovery of inflammatory exudative wounds: Since the porous structure of the polyurethane sponge can effectively absorb exudate and reduce local accumulation; coupled with the broad-spectrum antibacterial effect of the silver ions released by the silver-loaded kaolin, it helps to control wound infections; at the same time, zeolite can not only adsorb the odors and putrefactive substances in the exudate, but also balance the microenvironment of the wound surface to prevent the acidic or alkaline skin environment from affecting the wound healing; in addition, after the appropriate adsorption of the silver-loaded metakaolin hemostatic sponge, the wound surface protected by the silver-loaded metakaolin hemostatic sponge can remain moist without being overly dry, all of which are very conducive to cell regeneration and tissue repair.

[0030] 4. The short-cut silk fibers increase the biocompatibility of the material and improve the tensile strength of the sponge. At the same time, through hot pressing, the protruding fibers on the cut surface are toppled and attached to the cut surface, increasing the coverage area of the fibers on the cut surface, binding the exposed particles at the cut surface, better reducing the risk of shedding, and effectively preventing other potential hazards to the human body while implementing the hemostatic effect. Specific Embodiments

[0031] The following further elaborates on the present invention in conjunction with the embodiments, so that those skilled in the art can implement it with reference to the text of the specification.

[0032] It should be understood that terms such as "having", "comprising", and "including" used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0033] Unless otherwise specified, the test methods used in the following examples are all conventional methods. The materials, reagents, etc. used in the following examples can all be obtained from commercial channels unless otherwise specified. For those not indicating specific conditions in the following examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For those reagents or instruments not indicating the manufacturer, they are all conventional products that can be purchased commercially.

[0034] A silver-loaded metakaolin hemostatic sponge uses a foaming material as the base material, and the base material includes a mixture of silver-loaded metakaolin and zeolite embedded therein and short-cut fibers that are compatible with the human body; compared with kaolin, the mixture of silver-loaded metakaolin and zeolite can achieve a better comprehensive hemostatic effect.

[0035] The addition ratio of the silver-loaded metakaolin and zeolite mixture is 10wt%-40wt%; the addition ratio of the chopped fibers is 3wt%-15wt%. Among them, metakaolin with a particle size of ≥1.5μm is used. Metakaolin has high adsorption properties, can quickly adsorb the water and red blood cells in the blood to form blood clots, accelerate the natural blood coagulation of the human body, can also activate coagulation factor XII, initiate the coagulation cascade reaction, and has good biocompatibility, will not cause serious tissue reactions, and also has certain antibacterial properties.

[0036] The chopped fibers used are degummed mulberry silk chopped fibers. Silk fibers have good biocompatibility and better affinity for the human body. Compared with tussah silk, mulberry silk is finer and easier to shape.

[0037] In practical applications, the silver-loaded metakaolin hemostatic sponge is classified according to the mass ratio and different functions of zeolite and metakaolin. The silver-loaded metakaolin hemostatic sponge includes at least the following types:

[0038] Type A: Suitable for the high exudation stage of hemostasis or the initial stage of wound inflammation. Among them, the zeolite:metakaolin of the silver-loaded metakaolin and zeolite mixture is (1.5-3):1; the strong adsorption caused by the porous structure of zeolite can quickly adsorb blood to achieve the effect of rapid hemostasis. When used in the high exudation stage of the initial stage of wound inflammation, it can absorb a large amount of exudate within a certain period of time, and at the same time quickly release silver ions to inhibit infection. A certain dose of silver ions (such as 50ppm) can have a long-term bactericidal effect. If it is used for a long period of time, it is necessary to avoid too high a concentration of silver ions from inhibiting the migration of fibroblasts; however, if it is only used for short-term hemostasis, high-dose silver will not have obvious side effects on the human body, and products with a concentration far higher than 50ppm (such as 1000ppm) can be used to quickly sterilize. Since the silver-loaded metakaolin hemostatic sponge of Type A contains more zeolite, but due to the role of metakaolin and the addition of the foaming substrate and chopped fibers, the heat generation can be significantly reduced. Even when the ratio of zeolite:metakaolin is 3:1, the temperature acting on the wound at room temperature generally does not exceed 45°C.

[0039] Type B: Suitable for the granulation growth stage of the middle stage of wound inflammation. Among them, the zeolite:metakaolin of the silver-loaded metakaolin and zeolite mixture is (0.8-1.5):1; the silver-loaded metakaolin and zeolite mixture under this ratio can balance the adsorption and wound healing promotion functions. Zeolite continuously absorbs and controls bacteria, and kaolin promotes collagen deposition, shortening the healing cycle.

[0040] Type C: Suitable for the epithelialization stage in the late stage of wound repair. Among them, the zeolite:metakaolin in the silver-loaded metakaolin and zeolite composite material is (0.3 - 0.8):1. The silver-loaded metakaolin and zeolite composite material at this ratio accelerates angiogenesis by increasing the proportion of metakaolin and avoids wound dehydration caused by excessive adsorption. Since the wound has scabbed at this stage, a silver-loaded metakaolin hemostatic sponge product with a lower silver content or no silver can be used.

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

[0042] S1. Put 100 parts of polyol, 2 parts of water, 12 parts of additives, 60 parts of the silver-loaded metakaolin and zeolite composite material, 15 parts of chopped fibers, and 130 parts of isocyanate into a blender in sequence, mix them evenly and then foam to obtain the silver-loaded metakaolin hemostatic sponge embryo; the additives include 0.5 part of amine catalyst (PC-5), 1.5 parts of silicone oil, and 10 parts of cyclopentane.

[0043] S2. Cut the silver-loaded metakaolin hemostatic sponge embryo according to the required thickness to obtain the silver-loaded metakaolin hemostatic sponge embryo slice;

[0044] S3. After cutting, perform hot pressing treatment, at least on one side surface of the silver-loaded metakaolin hemostatic sponge embryo slice, to fix the particles exposed at the cut surface. After secondary cutting, a silver-loaded metakaolin hemostatic sponge in the required specification is obtained. There will be a large number of particles such as metakaolin exposed at the cut surface due to the cut section. Through hot pressing, the foaming substrate at the cut surface melts and combines with the exposed particles to achieve the effect of fixing the cut surface particles and preventing powder shedding. However, the melting of the foaming substrate at the cut surface will cause the silver-loaded metakaolin hemostatic sponge to absorb blood more slowly during hemostasis. Therefore, a method that does not melt the foaming substrate or does not cause large-area melting should be used to fix the cut surface particles.

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

[0046] Mix kaolin and zeolite in a mass ratio of 1:2 and put them into a ball mill for dry grinding for 60 min (the high adsorption of zeolite and kaolin can quickly absorb the moisture in the blood, concentrate the blood components, increase the relative concentration of local coagulation factors in the bleeding area, accelerate blood coagulation, and achieve the hemostatic effect). Then pour the silver nitrate aqueous solution (silver ion is one of the metal ions with the strongest bactericidal and antibacterial activities, has excellent antibacterial properties, and can kill a variety of bacteria, fungi and other microorganisms) into the mixture of kaolin and zeolite in a certain proportion (for example, finally making the content of silver nitrate in the silver-loaded metakaolin hemostatic sponge per cubic decimeter be 60 - 120 mg), and then wet grind for 60 min to make the silver ions fully and evenly adhere to the surfaces of metakaolin and zeolite particles, and then dry at 80 °C; since the dried material is easy to agglomerate, finally ball mill the dried material again for 30 min for dispersion and then use.

[0047] In S2, use a tungsten carbide blade to cut the original embryo of the silver-loaded metakaolin hemostatic sponge at a blade angle of 20°. In S2, the cutting speed is 2 m / min to reduce edge tearing, and at the same time, short-cut fiber protrusions are formed at the cut surface. At such a cutting angle, try to slow down the cutting speed so that while a part of the short-cut fibers at the cut surface are cut off, one end of the other part of the short-cut fibers can be pulled out from the substrate more, and the short-cut fibers at this part form short-cut fiber protrusions exposed on the cut surface. The more short-cut fiber protrusions there are, the better the fixing effect on the particles after being pressed down by heat.

[0048] The fiber length of the short-cut fibers is 0.5 - 5 mm, and the average fiber length of the short-cut fibers is not greater than the slice thickness of the original embryo of the silver-loaded metakaolin hemostatic sponge, so as to increase the number of short-cut fibers and form more short-cut fiber protrusions at the cut surface of the original embryo slice of the silver-loaded metakaolin hemostatic sponge.

[0049] In S2, use a roller press to roll one side surface of the original embryo slice of the silver-loaded metakaolin hemostatic sponge. The surface speed of the roller can be 1 - 2 m / min, the rolling pressure is 1000 Pa, and the surface temperature of the roller is 120 - 130 °C to make the silk fibers become soft and thus adhere to one side surface of the original embryo slice of the silver-loaded metakaolin hemostatic sponge. Then, under the condition of 80 - 100 °C, static pressure is applied to the original embryo slice of the silver-loaded metakaolin hemostatic sponge for 5 - 10 s, and the static pressure is 1000 - 2000 Pa, achieving the effect of shaping the silk fibers on one side surface of the original embryo slice of the silver-loaded metakaolin hemostatic sponge. In this way, the powder shedding rate on one side surface of the original embryo slice of the silver-loaded metakaolin hemostatic sponge can be controlled below 0.5%.

[0050] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those skilled in the art, additional modifications can be easily made. 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 silver-loaded metakaolin hemostatic sponge, characterized in that: The foaming material is used as the base material, and the base material includes a mixed material of silver-loaded metakaolin and zeolite and short-cut fibers that are friendly to 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%.

2. The silver-loaded metakaolin hemostatic sponge according to claim 1, characterized in that: The chopped fibers include degummed silk fibers.

3. The silver-loaded metakaolin hemostatic sponge according to claim 1, characterized in that: Based on the different mass ratios and functions of zeolite and metakaolin, the silver-loaded metakaolin hemostatic sponges include at least the following types: Type A: Suitable for hemostasis or the high exudation stage at the initial stage of wound inflammation, wherein the mixed material of silver-loaded metakaolin and zeolite is zeolite: metakaolin=(1.5-3):1; 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 = (0.8-1.5): 1; Type C: Suitable for the epithelialization stage in the later stage of wound repair, in which the mixed material of silver-loaded metakaolin and zeolite has a zeolite:metakaolin ratio of (0.3-0.8):

1.

4. A method for preparing the silver-loaded metakaolin hemostatic sponge according to claim 1, 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 mixer 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 according to the desired thickness to obtain the original embryo slice of the silver-loaded metakaolin hemostatic sponge; S3. After cutting, hot pressing is performed on at least one side of the original slice of the silver-loaded metakaolin hemostatic sponge to fix the particles exposed at the cut surface. After secondary cutting, a sheet of silver-loaded metakaolin hemostatic sponge of the required specifications is obtained.

5. The silver-loaded metakaolin hemostatic sponge according to claim 4, characterized in that: 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, and then the silver ion solution is poured into the ball mill for wet milling for 40-120 minutes, so that the silver ions are fully and evenly attached to the surface of the metakaolin and zeolite particles, and then dried at 50-80°C; since the dried material is easy to agglomerate, the dried material is finally ball-milled again for 20-30 minutes for dispersion and then set aside.

6. The silver-loaded metakaolin hemostatic sponge according to claim 4, characterized in that: In S2, the silver-loaded metakaolin hemostatic sponge embryo is cut at a blade angle of 15-20°.

7. The silver-loaded metakaolin hemostatic sponge according to claim 6, characterized in that: In S2, the cutting speed is not more than 2 m / min to reduce edge tearing and form short-cut fiber burrs at the cut surface.

8. The silver-loaded metakaolin hemostatic sponge according to claim 4, characterized in that: 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 section of the silver-loaded metakaolin hemostatic sponge embryo slice.

9. The silver-loaded metakaolin hemostatic sponge according to claim 4, characterized in that: 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.

10. The silver-loaded metakaolin hemostatic sponge according to claim 4, characterized in that: The auxiliary agents include physical foaming agents, catalysts and surfactants.