CN115368625B - Aramid fiber-assisted polyvinyl alcohol aerogel, and preparation method and application thereof - Google Patents

Aramid fiber-assisted polyvinyl alcohol aerogel, and preparation method and application thereof Download PDF

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CN115368625B
CN115368625B CN202211155645.3A CN202211155645A CN115368625B CN 115368625 B CN115368625 B CN 115368625B CN 202211155645 A CN202211155645 A CN 202211155645A CN 115368625 B CN115368625 B CN 115368625B
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polyvinyl alcohol
assisted
aramid fiber
aerogel
aramid
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CN115368625A (en
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张学同
杨晓旭
石楠
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • D—TEXTILES; PAPER
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    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract

The invention discloses an aramid fiber-assisted polyvinyl alcohol aerogel, and a preparation method and application thereof. The preparation method comprises the following steps: providing a composite dispersion liquid containing polyvinyl alcohol, aramid nanofibers and an organic solvent, and taking the composite dispersion liquid as a precursor to contact with water to realize sol-gel conversion so as to obtain aramid-assisted polyvinyl alcohol hydrogel; and then carrying out solvent replacement or not, and then drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel. The invention also provides an aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material, which consists of the auxiliary polyvinyl alcohol aerogel, has excellent hydrophilicity of polyvinyl alcohol and excellent mechanical property of aramid fiber nanofibers, and has a multi-stage pore structure with coexisting nanopores and micropores. The aerogel hemostatic material provided by the invention has good biocompatibility and high water absorption performance, has a rapid hemostatic effect, is simple in preparation process and low in energy consumption, is suitable for large-scale production, and has a wide application prospect.

Description

Aramid fiber-assisted polyvinyl alcohol aerogel, and preparation method and application thereof
Technical Field
The invention relates to an aramid fiber-assisted polyvinyl alcohol aerogel, in particular to an aramid fiber-assisted polyvinyl alcohol aerogel and a preparation method thereof, and application thereof in hemostatic materials, and belongs to the technical field of nano porous materials.
Background
Uncontrolled bleeding from wounds resulting from accidents, surgical bleeding, battlefield injuries, etc., is a major cause of death for wounded persons. It is reported that death by excessive bleeding occurs mostly before the wounded is sent to the emergency room. Thus, timely hemostasis after bleeding plays a decisive role in survival and recovery of wounded. The natural hemostatic process involves the initial thrombus formation induced by the activation and aggregation of blood clotting factors, including platelets and erythrocytes, followed by the activation of the coagulation cascade, forming a blood clot to achieve complete hemostasis. Hemostatic materials have been developed to accelerate the clotting process by different mechanisms, with hydrophilic porous materials absorbing moisture to concentrate the clotting factors in the blood, thereby activating the clotting cascade to accelerate hemostasis.
Existing hemostatic materials, such as powders, sponges, foams, films, and the like (biomatter. Sci.2020,8, 4396), are often prepared from hydrophilic polymers. The powder material is simple to prepare and has a certain hemostatic effect, but powder particles adhere to the surfaces of wounds and surrounding organs to cause debridement difficulty; the foam dressing has high viscosity, and the foam dressing can cause skin injury around wounds after being removed after being used; the sponge dressing is often fixed by using two layers of dressing or adhesive tape, is not easy to remove during replacement, and can cause secondary injury to wounds; the use of film dressings is not possible when the surrounding skin is fragile or infects wounds. The deficiency of the hemostatic materials makes the hemostatic materials with simple use and post-treatment represented by gauze widely applied to the scenes of emergency rescue, operation hemostasis and the like. The conventional medical gauze is a hemostatic material commonly used for treating superficial and small-volume wound hemorrhage, and although the hemostatic material can absorb blood at a wound, the gauze fiber does not have pores capable of absorbing blood and enriching blood cells, and the pores among the gauze fibers are far larger than the size of blood cells (about 2-10 μm), so that blood factors such as blood cells can flow freely and cannot be effectively enriched to activate a blood coagulation cascade, and the blood loss amount in the hemostatic process is often excessive (Nat. Commun.2019, 10, 5562). In order to improve the blood coagulation factor enrichment capability of gauze, patent CN 209301808U loads porous zeolite with nanometer pore diameter (1 nm) on the surface of gauze fiber, however, the loading amount of the porous material is limited (7 wt.% to 30 wt.%), and the hemostatic effect of the gauze is still limited. Therefore, preparing fibers containing abundant submicron pores and weaving into gauze is an effective way to promote the hemostatic effect of the material.
Aerogels are a typical nanoporous material prepared by wet gel removal of all solvents. In the process, the solid structure of the gel is preserved completely, comprises a network porous structure formed by mutually communicated or closed holes and is filled with gas, so that the aerogel has abundant mesopores, extremely low density and ultrahigh specific surface area, has pore size of between 2 and 50nm, and can block coagulation factors such as blood cells in the process of absorbing liquid in blood. If the aerogel is made into fibers and further woven into gauze, rapid water absorption and blood coagulation factor enrichment can be realized under the condition of improving the effective contact area. In recent years, a process for preparing aerogel fibers has been developed, and aerogel fibers (mate.today chem.2022, 23, 100736) can be prepared by wet spinning, reaction spinning, 3D printing, centrifugal spinning, and the like. Most aerogel fibers still have poor mechanical strength and, while they can be used as fillers or compounded with other fibers, it is difficult to prepare aerogel gauzes in large quantities by machine braiding. Aerogel fibers such as polyimide or aramid aerogel fibers having good mechanical properties are made of polymers containing benzene rings, and have insufficient biocompatibility and hydrophilicity. Therefore, there is no report in patent or literature on preparing aerogel hemostatic gauze from hydrophilic biocompatible polymers.
Polyvinyl alcohol is a representative water-soluble high molecular polymer, and has been proved to have good biocompatibility, biodegradability and mechanical properties by a large number of studies (j.adv.res.2017, 8, 217). In order to prepare the polyvinyl alcohol aerogel, a physical (freeze thawing method, i.e. forming intermolecular and intramolecular hydrogen bonds of the polyvinyl alcohol through freeze-thawing cycle, further forming hydrogel with a three-dimensional network structure) or chemical (using cross-linking agents such as boric acid, glutaraldehyde) cross-linking method is often adopted to form the polyvinyl alcohol hydrogel (New chem. Mater.2022, 50, 248), and then the polyvinyl alcohol aerogel is prepared through freeze drying, but most of the obtained polyvinyl alcohol aerogel is particle or block aerogel, so that the preparation time cost is higher, and the pore diameter is generally in the micron level. Since the water absorption driving force (capillary pressure) of a hydrophilic porous material is inversely proportional to its pore size, i.e., P c ～1/r pore (sci.adv.2018, 4, eaao7051), to enhance the water absorbing effect of the material, it is necessary to prepare polyvinyl alcohol aerogel fibers and gauze with nano-pore size. However, such materials have not been reported in the patent and literature.
Disclosure of Invention
The invention mainly aims to provide an aramid fiber-assisted polyvinyl alcohol aerogel and a preparation method thereof, so as to overcome the defects in the prior art.
The invention also aims to provide an aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material which has the advantages of high hydrophilicity, rapid water absorption and high-efficiency blood coagulation factor enrichment.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of polyvinyl alcohol aerogel assisted by aramid fibers, which comprises the following steps:
providing a composite dispersion comprising polyvinyl alcohol, aramid nanofibers, and an organic solvent;
the composite dispersion liquid is used as a precursor to be contacted with water to realize sol-gel conversion, so as to obtain aramid fiber-assisted polyvinyl alcohol hydrogel;
and optionally carrying out or not carrying out solvent replacement on the aramid fiber-assisted polyvinyl alcohol hydrogel, and then drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
In some embodiments, the method of making comprises: preparing a precursor with the temperature of 20-70 ℃ into a selected shape through extrusion and 3D printing processes, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
In other embodiments, the method of making comprises:
Carrying out wet spinning on a precursor with the temperature of 50-100 ℃ by taking water as a coagulating bath, and then adding water to obtain an aramid fiber-assisted polyvinyl alcohol hydrogel fiber; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel fiber.
The embodiment of the invention also provides the aramid fiber-assisted polyvinyl alcohol aerogel prepared by the preparation method, which comprises a three-dimensional porous network structure mainly composed of polyvinyl alcohol and aramid fiber nanofibers, wherein the three-dimensional porous network structure takes the aramid fiber nanofibers as a framework, and the polyvinyl alcohol is coated on the surfaces of the aramid fiber nanofibers.
The embodiment of the invention also provides application of the aramid fiber-assisted polyvinyl alcohol aerogel in preparing hemostatic materials.
Correspondingly, the embodiment of the invention also provides an aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material which consists of the aramid fiber-assisted polyvinyl alcohol aerogel and has a multistage pore structure with coexisting nano pores and micro pores; the density of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is 0.02-0.35 g/cm 3 The porosity is 60-98%, the thermal conductivity is 0.02-0.1W/m K, and the specific surface area is 50-800 m 2 And/g, the apparent contact angle with water is 10-85 degrees.
Compared with the prior art, the invention has the beneficial effects that:
1) The aramid fiber-assisted polyvinyl alcohol aerogel precursor can be used for preparing polyvinyl alcohol aerogel through different processing methods, including 3D printing and wet spinning to prepare aramid fiber-assisted polyvinyl alcohol aerogel; and a lower PVA concentration is used to obtain better mechanical properties, and meanwhile, the biocompatibility is ensured;
2) According to the preparation method, the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is prepared through supercritical drying, so that compared with the method, the efficiency of freeze drying is higher, and the nano pores of the aerogel are more uniform;
3) Compared with medical gauze, the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material provided by the invention has high porosity, high specific surface area and high water absorption, is more convenient to carry and post-treat compared with a granular aerogel hemostatic material, and has better flexibility and higher water permeability compared with a bulk aerogel hemostatic material;
4) According to the method for preparing the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material through 3D printing, the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material can be prepared through 3D printing in a non-braiding mode, and the preparation speed of the aerogel hemostatic gauze is improved.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIGS. 1a and 1b are, respectively, an optical photograph and a compression performance chart of an aramid-assisted polyvinyl alcohol aerogel obtained in example 1 of the present invention.
FIG. 2 is a scanning electron microscope topography of an aramid-assisted polyvinyl alcohol aerogel obtained in example 1 of the present invention.
Fig. 3a and 3b are optical photographs and tensile properties, respectively, of the aramid-assisted polyvinyl alcohol aerogel fiber obtained in example 2 of the present invention on a roll.
Fig. 4a and 4b are optical photographs of the 3D printing process of the aramid-assisted polyvinyl alcohol aerogel precursor in example 3 of the present invention.
FIG. 5 is a graph showing the interlayer morphology of the 3D printed aramid-assisted polyvinyl alcohol aerogel obtained in example 3 of the present invention.
FIG. 6 is a surface topography of a 3D printed aramid-assisted polyvinyl alcohol aerogel obtained in example 4 of the present invention.
FIGS. 7 a-7 c are optical photographs and fiber morphology graphs of aramid-assisted polyvinyl alcohol aerogel hemostatic gauze obtained in example 5 of the present invention.
FIG. 8 is a graph showing the water absorption performance of the aramid fiber-assisted polyvinyl alcohol hemostatic gauze obtained in example 6 of the present invention.
FIGS. 9a and 9b are graphs showing the microsphere enrichment capacities of the aramid-assisted polyvinyl alcohol hemostatic gauze and the commercial gauze, respectively, obtained in example 6 of the present invention.
FIGS. 10a and 10b are graphs showing in vitro hemostatic performance of aramid-assisted polyvinyl alcohol aerogel hemostatic gauze obtained in example 7 of the present invention.
FIGS. 11a and 11b are graphs showing in vivo hemostatic performance of aramid-assisted polyvinyl alcohol aerogel hemostatic gauze obtained in example 7 of the present invention.
FIGS. 12a and 12b are scanning electron microscope images showing the appearance of blood cell aggregation on the surface of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze obtained in example 7 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor provides a preparation method of the invention through long-term research, which mainly prepares the polyvinyl alcohol aerogel fiber through compounding the polyvinyl alcohol and the aramid nanofiber and assembles the polyvinyl alcohol aerogel fiber into the aerogel hemostatic gauze. The technical scheme, the implementation process, the principle and the like are further explained as follows.
The preparation method of the aramid fiber-assisted polyvinyl alcohol aerogel provided by one aspect of the embodiment of the invention comprises the following steps:
providing a composite dispersion comprising polyvinyl alcohol, aramid nanofibers, and an organic solvent;
the composite dispersion liquid is used as a precursor to be contacted with water to realize sol-gel conversion, so as to obtain aramid fiber-assisted polyvinyl alcohol hydrogel;
and optionally carrying out or not carrying out solvent replacement on the aramid fiber-assisted polyvinyl alcohol hydrogel, and then drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
In some embodiments, the method of making comprises:
adding polyvinyl alcohol into an organic solvent, and stirring for 0.5-40 h at a water bath of 30-90 ℃ to obtain a polyvinyl alcohol solution;
dispersing the aramid nanofibers in an organic solvent to obtain an aramid nanofiber dispersion;
mixing the polyvinyl alcohol solution and the aramid nanofiber dispersion liquid according to the mass ratio of (10-1) to 1, and stirring in a water bath at 30-90 ℃ for 0.2-40 h to obtain the composite dispersion liquid as a precursor.
In some embodiments, the concentration of polyvinyl alcohol in the polyvinyl alcohol solution is from 0.2 to 35wt%.
Further, the polyvinyl alcohol has a number average molecular weight of 5000-200000 and an alcoholysis degree of >99%.
In some embodiments, the concentration of aramid nanofibers in the aramid nanofiber dispersion is 0.1 to 15 weight percent.
Further, the aramid nanofiber dispersion may further include an alkaline substance providing an alkaline environment for preparing the aramid nanofiber dispersion, the alkaline substance including sodium hydroxide, or other organic base capable of being dissolved in an organic solvent, preferably potassium t-butoxide, but is not limited thereto.
Further, the diameter of the aramid nanofiber is 5-50 nm, and the aramid nanofiber is prepared by wet chemical stripping. The aramid nanofiber can form a framework of a gel network with excellent mechanical strength, and the polyvinyl alcohol is coated on the surface of the nanofiber through hydrogen bonding so as to improve the overall hydrophilicity and biocompatibility of the material.
Further, the organic solvent includes dimethyl sulfoxide, but is not limited thereto.
In some more specific embodiments, the method for preparing the aramid-assisted polyvinyl alcohol precursor comprises:
(1) Polyvinyl alcohol is added into dimethyl sulfoxide, stirred for 0.5 to 40 hours in a water bath at a temperature of between 30 and 90 ℃ to obtain a polyvinyl alcohol solution with a concentration of between 0.2 and 35 weight percent, and the lower PVA concentration is used to obtain better mechanical properties, and meanwhile, the biocompatibility is ensured.
(2) Dispersing aramid nano-fiber in dimethyl sulfoxide solution, and controlling the concentration to be 0.1-15 wt%.
(3) Polyvinyl alcohol and aramid nanofibers are mixed in dimethyl sulfoxide according to the mass ratio of (10-1): 1 stirring for 0.2-40 h in water bath at 30-90 ℃ (preferably 60-70 ℃) to obtain dark red aramid nanofiber-polyvinyl alcohol mixed solution as a precursor.
In some embodiments, the precursor solution has a concentration of 0.2 to 20wt%, a rapid reversible response temperature and shear stress, a viscosity of 100 to 10000 Pa-s at 20 to 50 ℃, and a yield stress of 100 to 10000Pa; the viscosity of the precursor solution is 1-10 Pa.s at 50-100 ℃, and the yield stress is 10-500 Pa. The precursor can be processed into aerogel hemostatic gauze through wet spinning and then braiding or non-braiding 3D printing, so that mass production of the aerogel hemostatic gauze is realized.
Further, the step (3) needs to be fully stirred in a closed state to prevent the water in the air from being absorbed to cause the gel to be advanced.
Further, the precursor solution in the step (3) may be stored in a closed state for more than 14 days to be used.
In some more specific embodiments, the method for preparing the aramid-assisted polyvinyl alcohol aerogel comprises:
(1) Preparing a composite dispersion liquid of polyvinyl alcohol and aramid nanofibers in dimethyl sulfoxide as a precursor;
(2) The precursor is contacted with water to realize sol-gel conversion, and after full gel, the aramid fiber-assisted polyvinyl alcohol hydrogel is obtained;
(3) And performing solvent replacement on the aramid fiber-assisted polyvinyl alcohol hydrogel in ethanol, and then performing supercritical drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel, or directly performing freeze drying on the aramid fiber-assisted polyvinyl alcohol hydrogel to obtain the aramid fiber-assisted polyvinyl alcohol aerogel. Most preferably, the aramid-assisted polyvinyl alcohol aerogel is prepared by supercritical drying.
Specifically, the aramid fiber-assisted polyvinyl alcohol aerogel can obtain better specific surface area, water absorption and hemostatic speed than freeze drying through supercritical drying preparation. And compared with freeze drying, the nano-pore of the aerogel is more uniform.
In some embodiments, the displacement solvent employed for the solvent displacement includes, but is not limited to, ethanol.
In some embodiments, the drying process includes any one of supercritical drying, freeze drying, and the like, preferably supercritical drying, but is not limited thereto.
In some more specific embodiments, the method for preparing the aramid-assisted polyvinyl alcohol aerogel comprises:
preparing a precursor with the temperature of 20-70 ℃ into a designed selected shape through extrusion and 3D printing processes, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel; and then carrying out solvent replacement and drying treatment (supercritical drying) on the obtained product by ethanol to obtain the aramid fiber-assisted polyvinyl alcohol aerogel with the designed shape.
In other more specific embodiments, the method for preparing the aramid fiber-assisted polyvinyl alcohol aerogel comprises:
carrying out wet spinning on a precursor with the temperature of 50-100 ℃ by taking water as a coagulating bath, and then adding water to obtain an aramid fiber-assisted polyvinyl alcohol hydrogel fiber; and then carrying out solvent replacement and drying treatment (supercritical drying) on the aramid fiber-assisted polyvinyl alcohol aerogel fiber.
Specifically, both of the above methods need to be performed in a dry environment, reducing the effect of moisture in the air on the processing process.
Specifically, when the gel and the solvent were replaced in water, the dark red precursor solution became a white yellowish hydrogel after the solvent was replaced in water, and the cut-out observation section showed that the gel was sufficiently obtained.
In some embodiments, the surface of the aramid fiber-assisted polyvinyl alcohol aerogel fiber prepared by the wet spinning has a compact layer with a thickness of 0.5-10 μm, and no obvious pores exist on the surface. The surface of the aramid fiber-assisted polyvinyl alcohol aerogel prepared by 3D printing has no compact layer, and the surface has uniform pores which are smaller than 1 mu m.
The compact layer is still an aramid fiber and polyvinyl alcohol compound, is close to compact when observed under an electron microscope, and the nanofibers are similarly stacked in parallel and compact to influence the diffusion speed of water to an aerogel network after contacting with blood. The mechanism of the formation of the dense layer is as follows: the aramid nanofibers with negative charges can diffuse in the direction of water or other solvents containing protons when encountering the water or other solvents, and form a compact layer after aggregation and gelation near the interface. After the compact layer is formed, water gradually diffuses into the interior, and is mutually dissolved with the solvent dimethyl sulfoxide, so that the diffusion effect of the nanofiber is not obvious, and the internal network structure is effectively reserved. And the 3D printing is carried out by adopting the gelled precursor, so that the diffusion and aggregation of the nanofibers are limited, a compact layer is basically absent, and the network structure is formed from outside to inside.
As another aspect of the technical scheme of the invention, the invention also relates to the aramid fiber-assisted polyvinyl alcohol aerogel prepared by the preparation method, wherein the aramid fiber-assisted polyvinyl alcohol aerogel comprises a three-dimensional porous network structure mainly composed of polyvinyl alcohol and aramid fiber nanofibers, and the three-dimensional porous network structure is a composite structure with the aramid fiber nanofibers as a framework and polyvinyl alcohol coated on the surfaces of the aramid fiber nanofibers.
As another aspect of the technical scheme, the invention also relates to application of the aramid fiber-assisted polyvinyl alcohol aerogel in preparing hemostatic materials.
Further, the hemostatic material includes any one of hemostatic gauze, hemostatic powder, hemostatic microspheres, hemostatic films, hemostatic sponge blocks, and the like, but is not limited thereto.
Correspondingly, another aspect of the embodiment of the invention also provides an aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material, which consists of the aramid fiber-assisted polyvinyl alcohol aerogel, and has excellent hydrophilicity of polyvinyl alcohol and excellent mechanical property of an aramid fiber nanofiber, and a multistage pore structure with coexisting nanopores and micropores.
Further, the density of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is 0.02-0.35 g/cm 3 The porosity is 60-98%, the thermal conductivity is 0.02-0.1W/m K, and the specific surface area is 50-800 m 2 And/g, the apparent contact angle with water is 10-85 degrees.
Further, the fibers of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material consist of aramid fiber-assisted polyvinyl alcohol aerogel, and the aerogel hemostatic material (such as hemostatic gauze) is prepared by weaving the aramid fiber-assisted polyvinyl alcohol aerogel fibers obtained by wet spinning, or the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material (such as hemostatic gauze) is prepared by 3D printing without weaving. The aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is prepared by 3D printing in a non-braiding mode, and the preparation speed of the aerogel hemostatic material can be improved.
More specifically, the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is formed by assembling aramid fiber-assisted polyvinyl alcohol aerogel fibers through braiding or direct 3D printing. The single polyvinyl alcohol aerogel fiber takes the aramid nanofiber as a skeleton, and the polyvinyl alcohol is coated on the surface of the aramid nanofiber skeleton under the action of hydrogen bonds, so that the single polyvinyl alcohol aerogel fiber has excellent hydrophilicity of the polyvinyl alcohol and excellent mechanical properties of the aramid nanofiber. Meanwhile, the nano holes (2-50 nm) of the aerogel fibers and the micro holes between the fibers form a multi-level hole structure, so that the polyvinyl alcohol aerogel hemostatic material has excellent water permeability, can quickly absorb water and has sufficient water absorption capacity, and micrometer-sized particles are effectively enriched.
Further, the tensile strength of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is 0.2-10 Mpa, the water absorption rate is 30% -2500%, and the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material can rapidly absorb moisture in blood and enrich blood coagulation components such as blood cells through a nano-pore structure, so that rapid hemostasis of wounds within 3 minutes is realized.
Further, through a mouse animal test, the haemostatic material of the polyvinyl alcohol aerogel assisted by the aramid fiber has a haemolysis rate of not more than 5 percent and a coagulation index of not more than 20 percent, and can be used as a rapid haemostatic material for trauma.
Further, the aramid-assisted polyvinyl alcohol aerogel hemostatic material may be an aramid-assisted polyvinyl alcohol aerogel hemostatic gauze, but is not limited thereto. The aerogel hemostatic gauze has the advantages of high water absorption rate of the aerogel and high permeability of the gauze, and can quickly absorb blood at a wound. Meanwhile, as the pores of the aerogel are far smaller than the size of blood cells, the moisture in the blood is ensured to be rapidly absorbed and blood cells and other coagulation factors which can trigger a coagulation cascade reaction are enriched, and the advantages enable the aramid-assisted polyvinyl alcohol aerogel gauze to realize the application of rapid hemostasis.
Furthermore, compared with medical gauze, the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze provided by the invention has high porosity, high specific surface area and high water absorption, is more convenient to carry and post-treat compared with a granular aerogel hemostatic material, and has better flexibility and higher water permeability compared with a bulk aerogel hemostatic material.
Further, in the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material, the polyvinyl alcohol and the aramid fiber realize good compounding through hydrogen bond interaction, and the hydroxyl on the polyvinyl alcohol side chain is a functional group forming a hydrogen bond, so that the polyvinyl alcohol with the alcoholysis degree higher than 99% is preferable. The higher the molecular weight, the more the polyvinyl alcohol molecules can be entangled with the more the aramid nanofibers, improving the overall strength of the network, so polyvinyl alcohol with a number average molecular weight above 70000 is preferred.
In conclusion, the aramid fiber-assisted polyvinyl alcohol aerogel can be used for trauma hemostasis application, and has the advantages of high hydrophilicity, rapid water absorption and high-efficiency blood coagulation factor enrichment. The aerogel hemostatic material has good biocompatibility and high water absorption performance, has a rapid hemostatic effect, is simple in preparation process and low in energy consumption, is suitable for large-scale production, and has a wide application prospect.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. It should be noted that the examples described below are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
The preparation of the aramid fiber-assisted polyvinyl alcohol aerogel comprises the following steps:
Step (1), preparing an aramid fiber-assisted polyvinyl alcohol aerogel precursor solution: 10g of polyvinyl alcohol (molecular weight: about 75000, alcoholysis degree: 99.1%) was added to 90g of dimethyl sulfoxide, and stirred in a water bath at 90℃for 2 hours to obtain a 10% strength by weight polyvinyl alcohol solution. 2g of aramid nanofiber and 2g of potassium tert-butoxide were added to 96g of dimethyl sulfoxide, and the mixture was mechanically stirred for 2 days to obtain an aramid nanofiber dispersion having a concentration of 2 wt%. Mixing 10wt% concentration polyvinyl alcohol solution and 2wt% concentration nanometer aramid fiber dispersion liquid according to equal mass, and stirring at 70 deg.c for 2 hr to obtain homogeneous nanometer auxiliary polyvinyl alcohol aerogel precursor solution.
Step (2), preparation of aramid fiber-assisted polyvinyl alcohol hydrogel: pouring the 70 ℃ aramid fiber-assisted polyvinyl alcohol aerogel precursor solution in the step (1) into a prepared mould, basically losing fluidity after the precursor solution is cooled to 25 ℃, and immersing the precursor solution into water with the volume being more than five times of that of the precursor solution for gelation. And (3) replacing water for six times every 2-4 hours to obtain the aramid fiber-assisted polyvinyl alcohol hydrogel.
Step (3), preparation of aramid fiber-assisted polyvinyl alcohol aerogel: taking the aramid fiber-assisted polyvinyl alcohol hydrogel obtained in the step (2) out of a die, displacing the die with an ethanol solvent, and then drying with supercritical carbon dioxide to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
The optical photograph of the aramid fiber-assisted polyvinyl alcohol aerogel prepared in the embodiment is shown in fig. 1a, the compressibility is shown in fig. 1b, and the microscopic morphology of the scanning electron microscope is shown in fig. 2.
Example 2
The preparation of the aramid fiber-assisted polyvinyl alcohol aerogel fiber by wet spinning comprises the following steps:
step (1), preparing an aramid fiber-assisted polyvinyl alcohol aerogel precursor solution: 10g of polyvinyl alcohol (molecular weight: about 145000, degree of alcoholysis: 99.2%) was added to 90g of dimethyl sulfoxide and stirred in a water bath at 90℃for 2 hours to obtain a 10% strength by weight polyvinyl alcohol solution. 1g of aramid fiber and 1g of potassium tert-butoxide were added to 98g of dimethyl sulfoxide, and the mixture was mechanically stirred for 1 day to obtain an aramid nanofiber dispersion having a concentration of 1 wt%. Mixing 10wt% concentration polyvinyl alcohol solution and 1wt% concentration nanometer aramid fiber dispersion liquid according to equal mass, and stirring at 70 deg.c for 2 hr to obtain homogeneous nanometer auxiliary polyvinyl alcohol aerogel precursor solution.
Step (2), preparation of aramid fiber-assisted polyvinyl alcohol hydrogel fiber: pouring the 70 ℃ aramid fiber-assisted polyvinyl alcohol aerogel precursor solution in the step (1) into a syringe, keeping the temperature of the syringe at 70 ℃, and extruding the precursor solution by using a peristaltic pump. The precursor solution was extruded through a 200 μm needle into the coagulation bath at a rate consistent with the collection rate. After the collection is finished, immersing the fiber into water with more than five times of the volume of the fiber, and replacing the water every 1-2 hours during the period, thereby obtaining the continuous aramid fiber-assisted polyvinyl alcohol hydrogel fiber.
Step (3), preparation of aramid fiber-assisted polyvinyl alcohol aerogel fibers: and (3) replacing the aramid fiber-assisted polyvinyl alcohol hydrogel fiber in the step (2) with an ethanol solvent, and then drying with supercritical carbon dioxide to obtain the aramid fiber-assisted polyvinyl alcohol aerogel fiber.
The optical photograph of the aramid-assisted polyvinyl alcohol aerogel fiber prepared in this example is shown in fig. 3a, and the mechanical properties are shown in fig. 3b.
Example 3
The preparation method of the aramid fiber-assisted polyvinyl alcohol aerogel by 3D printing without a cold table comprises the following steps of:
step (1), preparing an aramid fiber-assisted polyvinyl alcohol aerogel precursor solution: 4g of polyvinyl alcohol (molecular weight: about 5000, alcoholysis degree: 99.1%) was added to 96g of dimethyl sulfoxide, and stirred in a water bath at 60℃for 2 hours to obtain a polyvinyl alcohol solution having a concentration of 4% by weight. 4g of aramid fiber and 4g of potassium tert-butoxide were added to 92g of dimethyl sulfoxide, and the mixture was mechanically stirred for 4 days to obtain an aramid nanofiber dispersion having a concentration of 4 wt%. Mixing a polyvinyl alcohol solution with the concentration of 4wt% and an aramid nanofiber dispersion with the concentration of 4wt% according to equal mass, and stirring at 70 ℃ for 2 hours to obtain a uniform aramid-assisted polyvinyl alcohol aerogel precursor solution.
Step (2), preparation of aramid fiber-assisted polyvinyl alcohol ink: pouring the 70 ℃ aramid fiber-assisted polyvinyl alcohol aerogel precursor solution in the step (1) into a syringe of 3D printing equipment, sealing the syringe, and basically losing fluidity after the precursor solution is cooled to be used as 3D printing ink.
Step (3), 3D printing of aramid fiber-assisted polyvinyl alcohol gel: the shape to be 3D printed is set in a computer and input into a 3D printer. And (3) the temperature of the aramid fiber-assisted polyvinyl alcohol ink in the step (2) is kept at 40 ℃, the aramid fiber-assisted polyvinyl alcohol ink passes through a 500-mu m needle head under the pressure of 0.2-0.5 Mpa, the needle head performs 3D printing at the speed of 20mm/s, and the aramid fiber-assisted polyvinyl alcohol gel with a set shape is obtained after the printing is finished.
Step (4), preparing the 3D printed aramid fiber-assisted polyvinyl alcohol aerogel: immersing the aramid fiber-assisted polyvinyl alcohol gel printed in the step (3) into water with more than five times of the volume of the aramid fiber-assisted polyvinyl alcohol gel, and replacing the water for six times every 1-2 hours during the period to obtain the aramid fiber-assisted polyvinyl alcohol gel. And (3) replacing the aramid fiber-assisted polyvinyl alcohol hydrogel with an ethanol solvent, and then drying with supercritical carbon dioxide to obtain the 3D-printed aramid fiber-assisted polyvinyl alcohol aerogel with a set shape.
In this embodiment, the optical photographs of the precursor of the aramid fiber-assisted polyvinyl alcohol aerogel in the 3D printing process are shown in fig. 4a and fig. 4b, and the interlayer structure morphology of the 3D printing aramid fiber-assisted polyvinyl alcohol aerogel is shown in fig. 5.
Example 4
The preparation of the aramid fiber-assisted polyvinyl alcohol aerogel by 3D printing with a cooling table comprises the following steps:
step (1), preparing an aramid fiber-assisted polyvinyl alcohol aerogel precursor solution: 35g of polyvinyl alcohol (molecular weight: about 145000, degree of alcoholysis: 99.1%) was added to 65g of dimethyl sulfoxide and stirred in a water bath at 90℃for 0.5h to obtain a polyvinyl alcohol solution having a concentration of 35% by weight. 15g of aramid fiber and 5g of potassium tert-butoxide were added to 80g of dimethyl sulfoxide, and the mixture was mechanically stirred for 2 days to obtain an aramid nanofiber dispersion having a concentration of 15 wt%. Mixing a polyvinyl alcohol solution with the concentration of 35wt% and an aramid nanofiber dispersion with the concentration of 15wt% according to equal mass, and stirring at 90 ℃ for 0.2h to obtain a uniform aramid-assisted polyvinyl alcohol aerogel precursor solution.
Step (2), preparation of aramid fiber-assisted polyvinyl alcohol ink: pouring the 70 ℃ aramid fiber-assisted polyvinyl alcohol aerogel precursor solution in the step (1) into a needle cylinder of 3D printing equipment to serve as ink, and cooling is not needed to be used for 3D printing with a cooling table.
Step (3), 3D printing of aramid fiber-assisted polyvinyl alcohol gel: the shape to be 3D printed is set in a computer and input into a 3D printer. And (3) maintaining the temperature of the aramid fiber-assisted polyvinyl alcohol ink in the step (2) at 70 ℃, enabling the aramid fiber-assisted polyvinyl alcohol ink to pass through a 500-mu m needle head under the pressure of 0.2-0.5 Mpa, setting the temperature of a cooling table to be-80 ℃, and performing 3D printing on the needle head at the speed of 100mm/s to obtain the aramid fiber-assisted polyvinyl alcohol gel with the set shape after the printing is finished.
Step (4), preparing the 3D printed aramid fiber-assisted polyvinyl alcohol aerogel: immersing the aramid fiber-assisted polyvinyl alcohol gel printed in the step (3) into water with more than five times of the volume of the aramid fiber-assisted polyvinyl alcohol gel, and replacing the water for six times every 1-2 hours during the period to obtain the aramid fiber-assisted polyvinyl alcohol gel. And (3) replacing the aramid fiber-assisted polyvinyl alcohol hydrogel with an ethanol solvent, and then drying with supercritical carbon dioxide to obtain the 3D-printed aramid fiber-assisted polyvinyl alcohol aerogel with a set shape.
The surface morphology of the 3D printed aramid-assisted polyvinyl alcohol aerogel prepared in this example is shown in fig. 6.
Example 5
The preparation method of the aramid fiber-assisted polyvinyl alcohol aerogel gauze by 3D printing comprises the following steps of:
step (1), preparing an aramid fiber-assisted polyvinyl alcohol aerogel precursor solution: 0.2g of polyvinyl alcohol (molecular weight: about 200000, alcoholysis degree: 99.2%) was added to 99.8g of dimethyl sulfoxide, and stirred in a water bath at 30℃for 40 hours to obtain a polyvinyl alcohol solution having a concentration of 0.2% by weight. 0.1g of aramid fiber and 3.9g of potassium t-butoxide were added to 96g of dimethyl sulfoxide, and the mixture was mechanically stirred for 2 days to obtain an aramid nanofiber dispersion having a concentration of 0.1 wt%. Mixing a polyvinyl alcohol solution with the concentration of 0.2 weight percent and an aramid nanofiber dispersion with the concentration of 0.1 weight percent according to the equal mass ratio, and stirring for 40 hours at the temperature of 30 ℃ to obtain a uniform aramid-assisted polyvinyl alcohol aerogel precursor solution.
Step (2), preparation of aramid fiber-assisted polyvinyl alcohol ink: pouring the 70 ℃ aramid fiber-assisted polyvinyl alcohol aerogel precursor solution in the step (1) into a syringe of 3D printing equipment, sealing the syringe, and basically losing fluidity after the precursor solution is cooled to be used as 3D printing ink.
Step (3), 3D printing of an aramid fiber-assisted polyvinyl alcohol gauze-shaped gel: the gauze shape required for 3D printing is set in a computer and input into a 3D printer. And (3) the temperature of the aramid fiber-assisted polyvinyl alcohol ink in the step (2) is kept at 45 ℃, the aramid fiber-assisted polyvinyl alcohol ink passes through a 500-mu m needle head under the pressure of 0.2-0.5 Mpa, the needle head performs 3D printing at the speed of 20mm/s, and the aramid fiber-assisted polyvinyl alcohol gel in a gauze shape is obtained after the printing is finished.
Step (4), preparation of 3D printed aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze: immersing the aramid fiber-assisted polyvinyl alcohol gauze gel printed in the step (3) into water with more than five times of the volume of the aramid fiber-assisted polyvinyl alcohol gauze gel, and replacing the water for six times every 1-2 hours during the period to obtain the aramid fiber-assisted polyvinyl alcohol hydrogel gauze. And (3) replacing the aramid fiber-assisted polyvinyl alcohol hydrogel gauze with an ethanol solvent, and then drying with supercritical carbon dioxide to obtain the 3D printed aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze.
The optical photographs and fiber morphology of the aramid-assisted polyvinyl alcohol aerogel hemostatic gauze prepared in this example are shown in fig. 7a, 7b and 7c.
Example 6
The performance test of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze comprises the following steps:
step (1), the preparation process of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze in the present example 6 refers to the preparation process of example 5, and the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze made of 500 μm yarn is prepared.
And (2) researching the water absorption rate of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze in the step (1), comparing the water absorption rate with commercial gauze Quick Combat Gauze, and measuring the water absorption rate of the gauze after the gauze is soaked in water for different times. The measured maximum water absorption rate of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze is 1138%, and the water absorption rate is higher than that of commercial gauze.
And (3) researching the microsphere enrichment capability of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze in the step (1), comparing by using commercial gauze Quick Combat Gauze, and measuring the diffusion condition of the dispersion liquid containing the micron-sized dyed microspheres drop by drop on the gauze. The measurement shows that the diffusion diameter of the aerogel gauze is about 0.76cm and is lower than the diffusion diameter of the commercial gauze by 1.3cm, which indicates that the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze can aggregate micro-particles such as microspheres more quickly.
The water absorption properties of the aramid-assisted polyvinyl alcohol hemostatic gauze in this example are shown in fig. 8, and the microsphere enrichment ability of the gauze with commercial gauze is shown in fig. 9a and 9b.
Example 7
The performance test of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze comprises the following steps:
step (1), the preparation process of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze in the present example 7 refers to the preparation process of example 5, and the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze made of 500 μm yarn is prepared.
And (2) researching the in-vitro and in-vivo hemostatic performances of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze in the step (1). The haemostatic gauze of the aramid fiber-assisted polyvinyl alcohol aerogel is tested by using rat blood, the haemostatic gauze has a haemolysis rate of 2.3 percent and an extracorporeal coagulation index of 16+/-0.2 percent. The rat liver laceration model is selected to verify the hemostatic performance of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze on a non-compressive wound, and the hemostatic time and blood loss of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze are respectively 60+/-4 s and 0.07+/-0.01 g, which indicates that the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze has excellent hemostatic potential and has better performance in all aspects than that of commercial gauze Quick Combat Gauze of a control group.
And (3) observing the surface of the gauze contacted with the wound in the step (2) by using a scanning electron microscope, wherein the aggregation of blood cells can be obviously observed.
The in vitro hemostatic performance of the aramid-assisted polyvinyl alcohol hemostatic gauze in this example is shown in fig. 10a and 10b, the in vivo hemostatic performance is shown in fig. 11a and 11b, and blood cells are accumulated on the surface of the gauze as shown in fig. 12a and 12b.
TABLE 1 Performance parameters of the aramid-assisted polyvinyl alcohol aerogels obtained in examples 1-5
Through examples 1-7, it can be found that the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze obtained by the technical scheme of the invention has low density, high specific surface area and low thermal conductivity after a small amount of aramid fiber nanofibers are added, has good biocompatibility and high water absorption performance, can be used for rapidly aggregating blood cells to achieve rapid hemostasis of wounds, and is simple in preparation process and easy for mass production.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (36)

1. Use of an aramid-assisted polyvinyl alcohol aerogel in the preparation of a hemostatic material, wherein the preparation method of the aramid-assisted polyvinyl alcohol aerogel comprises the following steps:
providing a composite dispersion liquid containing polyvinyl alcohol, aramid nanofibers and an organic solvent, wherein the mass ratio of the polyvinyl alcohol to the aramid nanofibers is (10-1): 1, the number average molecular weight of the polyvinyl alcohol is 5000-200000, the alcoholysis degree is more than 99%, and the diameter of the aramid nanofiber is 5-50 nm;
the composite dispersion liquid is used as a precursor solution to be contacted with water, so that sol-gel conversion is realized, and the polyvinyl alcohol hydrogel assisted by aramid fibers is obtained;
and optionally carrying out or not carrying out solvent replacement on the aramid fiber-assisted polyvinyl alcohol hydrogel, and then drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
2. Use according to claim 1, characterized in that the preparation method comprises:
adding polyvinyl alcohol into an organic solvent, and stirring for 0.5-40 h at the temperature of 30-90 ℃ in a water bath to obtain a polyvinyl alcohol solution;
dispersing the aramid nanofibers in an organic solvent to obtain an aramid nanofiber dispersion;
and mixing the polyvinyl alcohol solution and the aramid nanofiber dispersion liquid, and stirring in a water bath at 30-90 ℃ for 0.2-40 h to obtain the composite dispersion liquid.
3. Use according to claim 2, characterized in that: the concentration of the polyvinyl alcohol in the polyvinyl alcohol solution is 0.2-35 wt%.
4. Use according to claim 2, characterized in that: the concentration of the aramid nanofibers in the aramid nanofiber dispersion is 0.1-15 wt%.
5. Use according to claim 2, characterized in that: the aramid nanofiber dispersion also includes an alkaline substance including sodium hydroxide or an organic base capable of being dissolved in an organic solvent.
6. Use according to claim 5, characterized in that: the alkaline substance is potassium tert-butoxide.
7. Use according to claim 2 or 5, characterized in that: the organic solvent comprises dimethyl sulfoxide.
8. Use according to claim 1 or 2, characterized in that: the concentration of the precursor solution is 0.2-20wt%, the temperature and the shear stress can be quickly and reversibly responded, the viscosity of the precursor solution in the range of 20-50 ℃ is 100-10000 Pa.s, and the yield stress is 100-10000 Pa; the viscosity of the precursor solution is 1-10 Pa.s at 50-100 ℃, and the yield stress is 10-500 Pa.
9. Use according to claim 1, characterized in that the preparation method comprises: preparing the precursor solution with the temperature of 20-70 ℃ into a selected shape through extrusion and 3D printing processes, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
10. Use according to claim 9, characterized in that: the pore space of the surface of the aramid fiber-assisted polyvinyl alcohol aerogel prepared by 3D printing is smaller than 1 mu m.
11. Use according to claim 1, characterized in that the preparation method comprises: carrying out wet spinning on the precursor solution with the temperature of 50-100 ℃ by taking water as a coagulating bath, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel fibers; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel fiber.
12. Use according to claim 11, characterized in that: the surface of the aramid fiber-assisted polyvinyl alcohol aerogel fiber prepared by the wet spinning is provided with a compact layer with the thickness of 0.5-10 mu m.
13. Use according to claim 11, characterized in that: the displacement solvent used for the solvent displacement includes ethanol.
14. Use according to claim 11, characterized in that: the drying treatment comprises any one of supercritical drying and freeze drying.
15. Use according to claim 14, characterized in that: the drying treatment is supercritical drying.
16. Use according to claim 1, characterized in that: the aramid fiber-assisted polyvinyl alcohol aerogel comprises a three-dimensional porous network structure, wherein the three-dimensional porous network structure takes aramid fiber as a framework, and polyvinyl alcohol is coated on the surface of the aramid fiber.
17. Use according to claim 1, characterized in that: the hemostatic material comprises any one of hemostatic gauze, hemostatic powder, hemostatic microspheres, hemostatic films and hemostatic sponge blocks.
18. An aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is characterized in that itThe polyvinyl alcohol aerogel is composed of polyvinyl alcohol aerogel assisted by aramid fiber and has a multi-level pore structure with coexisting nano pores and micro pores; the density of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is 0.02-0.35 g/cm 3 Porosity of 60-98%, thermal conductivity of 0.02-0.1W/m K, specific surface area of 50-800 m 2 Per gram, the apparent contact angle with water is 10-85 degrees;
the preparation method of the aramid fiber-assisted polyvinyl alcohol aerogel comprises the following steps:
providing a composite dispersion liquid containing polyvinyl alcohol, aramid nanofibers and an organic solvent, wherein the mass ratio of the polyvinyl alcohol to the aramid nanofibers is (10-1): 1, the number average molecular weight of the polyvinyl alcohol is 5000-200000, the alcoholysis degree is more than 99%, and the diameter of the aramid nanofiber is 5-50 nm;
the composite dispersion liquid is used as a precursor solution to be contacted with water, so that sol-gel conversion is realized, and the polyvinyl alcohol hydrogel assisted by aramid fibers is obtained;
And optionally carrying out or not carrying out solvent replacement on the aramid fiber-assisted polyvinyl alcohol hydrogel, and then drying to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
19. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein: the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is prepared by 3D printing of the aramid fiber-assisted polyvinyl alcohol aerogel, or is prepared by braiding the aramid fiber-assisted polyvinyl alcohol aerogel fibers.
20. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein: the tensile strength of the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material is 0.2-10 Mpa, and the water absorption rate is 30% -2500%.
21. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein: the haemostatic material of the polyvinyl alcohol aerogel assisted by the aramid fiber has the haemolysis rate of not more than 5 percent and the coagulation index of not more than 20 percent.
22. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein: the aramid fiber-assisted polyvinyl alcohol aerogel hemostatic material comprises aramid fiber-assisted polyvinyl alcohol aerogel hemostatic gauze.
23. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein the method of making comprises:
adding polyvinyl alcohol into an organic solvent, and stirring for 0.5-40 h at the temperature of 30-90 ℃ in a water bath to obtain a polyvinyl alcohol solution;
dispersing the aramid nanofibers in an organic solvent to obtain an aramid nanofiber dispersion;
and mixing the polyvinyl alcohol solution and the aramid nanofiber dispersion liquid, and stirring in a water bath at 30-90 ℃ for 0.2-40 h to obtain the composite dispersion liquid.
24. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 23, wherein: the concentration of the polyvinyl alcohol in the polyvinyl alcohol solution is 0.2-35 wt%.
25. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 23, wherein: the concentration of the aramid nanofibers in the aramid nanofiber dispersion is 0.1-15 wt%.
26. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 23, wherein: the aramid nanofiber dispersion also includes an alkaline substance including sodium hydroxide or an organic base capable of being dissolved in an organic solvent.
27. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 26, wherein: the alkaline substance is potassium tert-butoxide.
28. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 23 or 26, wherein: the organic solvent comprises dimethyl sulfoxide.
29. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18 or 23, wherein: the concentration of the precursor solution is 0.2-20wt%, the temperature and the shear stress can be quickly and reversibly responded, the viscosity of the precursor solution in the range of 20-50 ℃ is 100-10000 Pa.s, and the yield stress is 100-10000 Pa; the viscosity of the precursor solution is 1-10 Pa.s at 50-100 ℃, and the yield stress is 10-500 Pa.
30. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein the method of making comprises: preparing the precursor solution with the temperature of 20-70 ℃ into a selected shape through extrusion and 3D printing processes, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel.
31. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 30 wherein: the pore space of the surface of the aramid fiber-assisted polyvinyl alcohol aerogel prepared by 3D printing is smaller than 1 mu m.
32. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 18, wherein the method of making comprises: carrying out wet spinning on the precursor solution with the temperature of 50-100 ℃ by taking water as a coagulating bath, and then adding water to obtain aramid fiber-assisted polyvinyl alcohol hydrogel fibers; and then carrying out solvent replacement and drying treatment to obtain the aramid fiber-assisted polyvinyl alcohol aerogel fiber.
33. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 32, wherein: the surface of the aramid fiber-assisted polyvinyl alcohol aerogel fiber prepared by the wet spinning is provided with a compact layer with the thickness of 0.5-10 mu m.
34. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 32, wherein: the displacement solvent used for the solvent displacement includes ethanol.
35. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 32, wherein: the drying treatment comprises any one of supercritical drying and freeze drying.
36. The aramid fiber assisted polyvinyl alcohol aerogel hemostatic material of claim 35 wherein: the drying treatment is supercritical drying.
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